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Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform. Gd(OTf) 3 -Catalyzed the Synthesis of Geranyl Esters for the Intramolecular Radical Cyclization of their Epoxides Mediated by Titanocene(III) William H. García Santos Carlos E. Puerto Galvis and Vladimir V. Kouznetsov* Laboratorio de Química Orgánica y Biomolecular, Universidad Industrial de Santander, Parque Tecnologico Guatiguara, Km 2 via refugio, Piedecuesta, A.A. 681011, Colombia. * [email protected]; [email protected]. ELECTRONIC SUPPORTING INFORMATION List of contents Pages 1. Reagents. ESI-2 2. Characterization data of all synthesized geranyl esters 12a-12t ESI-3 3. Characterization data of all synthesized 6,7-epoxy geranyl esters 13a-13k ESI-8 4. Characterization data of all synthesized (8-hydroxy-9,9-dimethyl-5- methylene cyclohexyl)methyl esters 14a-14h ESI-12 5. Extraction and characterization of the essential oil of palmarosa (Cymbopogon martinii) ESI-16 6. Copies of 1 H NMR, 13 C NMR, DEPT-135, COSY, HSQC and HMBC charts of the synthesized (E)-3,7-dimethylocta-2,6-dien-1-yl esters 12a-12p. ESI-17 7. Copies of 1 H NMR, 13 C NMR, DEPT-135, COSY, HSQC and HMBC charts of the synthesized (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl esters 13a-13k. ESI-40 8. Copies of 1 H NMR, 13 C NMR, DEPT-135, COSY, HSQC and HMBC charts of the synthesized (8-hydroxy-9,9-dimethyl-5-methylenecyclohexyl) methyl esters 14a-14h. ESI-56 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2014

Gd-Catalyzed the Synthesis of Geranyl Esters for their ... the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform. Gd(OTf)3-Catalyzed the Synthesis of

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Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

Gd(OTf)3-Catalyzed the Synthesis of Geranyl Esters for

the Intramolecular Radical Cyclization of their Epoxides

Mediated by Titanocene(III)

William H. García Santos Carlos E. Puerto Galvis and Vladimir V.

Kouznetsov*

Laboratorio de Química Orgánica y Biomolecular, Universidad Industrial de Santander,

Parque Tecnologico Guatiguara, Km 2 via refugio, Piedecuesta, A.A. 681011, Colombia.

* [email protected]; [email protected].

ELECTRONIC SUPPORTING INFORMATION

List of contents Pages

1. Reagents. ESI-2

2. Characterization data of all synthesized geranyl esters 12a-12t ESI-3

3. Characterization data of all synthesized 6,7-epoxy geranyl esters 13a-13k ESI-8

4. Characterization data of all synthesized (8-hydroxy-9,9-dimethyl-5-

methylene cyclohexyl)methyl esters 14a-14h

ESI-12

5. Extraction and characterization of the essential oil of palmarosa

(Cymbopogon martinii)

ESI-16

6. Copies of 1H NMR, 13C NMR, DEPT-135, COSY, HSQC and HMBC charts

of the synthesized (E)-3,7-dimethylocta-2,6-dien-1-yl esters 12a-12p.

ESI-17

7. Copies of 1H NMR, 13C NMR, DEPT-135, COSY, HSQC and HMBC charts

of the synthesized (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl esters 13a-13k.

ESI-40

8. Copies of 1H NMR, 13C NMR, DEPT-135, COSY, HSQC and HMBC charts

of the synthesized (8-hydroxy-9,9-dimethyl-5-methylenecyclohexyl) methyl

esters 14a-14h.

ESI-56

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2014

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-2

1. Reagents

Geraniol: Was purchased from Aldrich and used as received.

Triphenylphosphine: Was purchased from Aldrich and used as received.

Imidazole: Was purchased from Merck and used as received.

2-Methylimidazole: Was purchased from Aldrich and used as received.

Iodine: Was purchased from Aldrich and used as received.

Cinnamic acid: Was purchased from Aldrich and used as received.

Geranic acid: Was purchased from Aldrich and used as received.

Feluric acid: Was purchased from Aldrich and used as received.

Vanillic acid: Was purchased from Aldrich and used as received.

3,4,5-Trimethoxycinnamic acid: Was purchased from Aldrich and used as received.

3,4-Dimethoxycinnamic acid: Was purchased from Aldrich and used as received.

Nicotinic acid: Was purchased from Aldrich and used as received.

m-CPBA: Was purchased from Aldrich and used as received.

THF anhydrous: Was purchased from Alfa Aesar and used as received.

CH2Cl2: Was purchased from Alfa Aesar and used as received.

Pyridine: Was purchased from Aldrich and used as received.

Pyrrolidone: Was purchased from Aldrich and used as received.

Cp2TiCl2: Was purchased from Alfa Aesar and used as received.

Mn: Was purchased from Alfa Aesar and used as received.

Triethylamine: Was purchased from Alfa Aesar and used as received.

Silica gel 60 (0.063-0.200 mm) 70-230 mesh: Was purchased from Merck and used as

received.

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-3

2. Characterization data of all synthesized geranil esters 12a-12t

(E)-3,7-dimethylocta-2,6-dien-1-yl acetate (12a): Colorless oil (0.18 g, 0.94 mmol,

93%), Rf [hexane-EtOAc 15:1] = 0.7; IR (ATR, cm-1): 2922 (CH), 1738 (C=O), 1688

(C=C), 1229 (C-O), 831 (C=C-H); NMR (400 MHz, CDCl3), δ(ppm): 5.32 (1H, td, J = 7.1, 1.0

Hz, 4-H), 5.05 (1H, td, J = 6.7, 1.0 Hz, 8-H), 4.56 (2H, d, J = 7.2 Hz, O-CH2-), 2.11–

2.00 (4H, m, -CH2-), 2.03 (3H, s, COCH3), 1.67 (3H, s, 12-CH3), 1.65 (3H, s, 10-CH3),

1.57 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 171.1, 142.3, 131.8, 123.7

(+), 118.2 (+), 61.4 (-), 39.5 (-), 26.3 (-), 25.7 (+), 21.1 (+), 17.7 (+), 16.5 (+); GC: Rt=

48.963 min, MS (EI), m/z (%): 196 (M+·, 37), 127 (40), 81 (41), 73 (22), 69 (100), 45

(64); HRMS (ESI+): m/z: calcd for C12H21O2 ([M+H]+) 197.1536, found: 197.1538;

calcd for C12H20NaO2 ([M+Na]+): 219.1356, found: 219.1359.

(E)-3,7-dimethylocta-2,6-dien-1-yl-(E)-3,7-dimethylocta-2,6-dienoate (12b): Colorless

oil (0.15 g, 0.49 mmol, 75%), Rf [hexane-EtOAc 20:1] = 0.65; IR (ATR, cm-1): 2921

(CH), 1671 (C=O), 1612 (C=C), 1246 (C-O), 754 (C=C-H); 1H NMR (400 MHz, CDCl3),

δ(ppm): 6.97 (1H, dd, J = 8.3, 1.0 Hz, 2’-HAr), 6.87 (1H, td, J = 7.8, 1.0 Hz, 6’-HAr), 5.46

(1H, t, J = 7.0 Hz, 4-H), 5.11–5.07 (1H, m, 8-H), 4.86 (2H, d, J = 7.1 Hz, O-CH2-),

2.17–2.03 (8H, m, -CH2-), 1.77 (6H, s, 10’-CH3, 12-CH3), 1.67 (6H, s, 8’-CH3, 10-CH3),

1.60 (6H, s, 9’-CH3, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 161.6, 143.4, 132.1,

123.7 (+), 117.6 (+), 62.3 (-), 39.6 (-), 26.3 (-), 25.8 (+), 17.8 (+), 16.7 (+); GC: Rt=

51.847 min, MS (EI), m/z (%): 304 (M+·, 28), 235 (32), 167 (44), 83 (56), 69 (100);

HRMS (ESI+): m/z: calcd for C20H33O2 ([M+H]+) 305.2475, found: 305.2473; calcd for

C20H32NaO2 ([M+Na]+) 327.2295, found: 327.2291.

(±)-(E)-3,7-dimethylocta-2,6-dien-1-yl-5-(1,2-dithiolan-3-yl)pentanoate (12c): Yellow

oil (0.126 g, 0.353 mmol, 63%), Rf [hexane-EtOAc 15:1] = 0.5; IR (ATR cm-1): 2925

(CH), 1728 (C=O), 1636 (C=C), 1443 (C-S), 1228 (C-O), 753 (C-S); 1H NMR (400 MHz,

CDCl3), δ(ppm): 5.35–5.31 (1H, m, 4-H), 5.07 (td, J = 6.6, 0.9 Hz, 1H, 8-H), 4.58 (2H, d,

J = 7.1 Hz, -CH2-), 3.56 (1H, dq, J = 8.3, 6.5 Hz, 6’-H), 3.21–3.07 (2H, m, 8’-H), 2.45

(1H, dt, J = 12.2, 6.6 Hz, 7a’-H), 2.32 (2H, t, J = 7.4 Hz, 2’-H), 2.12–2.01 (4H, m, CH2),

1.90 (1H, dt, J = 19.7, 7.0 Hz, 7b’-H), 1.69 (3H, s, 12-CH3), 1.67 (3H, s, 10-CH3), 1.65–

1.61 (4H, m, 3’-H, 4’-H), 1.59 (3H, s, 11-CH3), 1.54–1.39 (2H, m, 5’-H); 13C NMR (101

MHz, CDCl3), δ(ppm): 173.7, 142.4, 131.9, 123.8 (-), 118.3 (+), 61.4 (-), 56.4 (+), 40.3 (-),

39.6 (-), 38.6 (-), 34.7 (-), 34.2 (-), 28.9 (-), 26.3 (-), 25.8 (+), 24.8 (-), 17.8 (+), 16.6 (+);

GC: Rt= 53.971 min, MS (EI), m/z (%): 342 (M+·, 31), 206 (32), 81 (44), 69 (100), 67

(28), 41 (56); HRMS (ESI+): m/z: calcd for C18H31O2S2 ([M+H]+) 343.1760, found:

343.1763; calcd for C18H30NaO2S2 ([M+Na]+) 365.1579, found: 365.1580.

(E)-3,7-dimethylocta-2,6-dien-1-yl-benzoate (12d): Colorless oil (0.17 g, 0.66 mmol,

85%), Rf: [hexane-EtOAc 15:1] = 0.6; IR(ATR cm-1): 2923 (CH), 1718 (C=O), 1602

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-4

(C=C), 1270 (C-O), 712 (C=C-H); 1H NMR (400 MHz, CDCl3), δ(ppm): 8.06–8.02 (2H, m,

3’-HAr, 4’-HAr), 7.58–7.51 (1H, m, 7’-HAr), 7.42 (2H, t, J = 7.7 Hz, 5’-HAr, 6’-HAr), 5.49

(1H, dtd, J = 8.0, 6.9, 1.1 Hz, 4-H), 5.10–5.07 (1H, m, 8-H), 4.84 (2H, d, J = 7.1 Hz, -

CH2-), 2.09 (4H, td, J = 12.1, 5.7 Hz, -CH2-), 1.76 (3H, s, 12-CH3), 1.67 (3H, s, 10-

CH3), 1.60 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): δ 166.8, 142.5, 132.9

(+), 131.9, 130.5 (+), 129.6 (+), 128.4 (+), 123.8 (+), 118.4 (+), 62.0 (-), 39.6 (-), 25.7

(+), 17.8 (+), 16.6 (+); GC: Rt= 38.290 min, MS (EI), m/z (%): 258 (M+·, 38), 105 (100),

69 (98), 68 (59), 77 (53), 41 (44); HRMS (ESI+): m/z: calcd for C17H22NaO2 ([M+Na]+)

281.1512, found: 281.1509; calcd for C17H22KO2 ([M+K]+) 297.1251, found: 297.1255.

(E)-3,7-dimethylocta-2,6-dien-1-yl-2-chlorobenzoate (12e): Pale pink oil (0.16 g, 0.55

mmol, 82%), Rf: [hexane-EtOAc 15:1] = 0.5; IR(ATR, cm-1): 2926 (CH), 1716 (C=O),

1610 (C=C), 1271 (C-O), 716 (C=C-H); 1H NMR (400 MHz, CDCl3), δ(ppm): 7.68 (1H, d, J

= 7.1 Hz, 4’-HAr), 7.28 (2H, d, J = 4.1 Hz, 6’-HAr, 7’-HAr), 7.18–7.14 (1H, m, 5’-HAr),

5.43–5.39 (1H, m, 4-H), 5.14–5.11 (1H, m, 8-H), 4.80 (2H, d, J = 7.1 Hz, -CH2-), 1.96–

1.87 (4H, m, -CH2-), 1.75 (3H, s, 12-CH3), 1.70 (3H, s, 10-CH3), 1.69 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 166.8, 142.5, 132.9 (+), 131.9, 130.5 (+), 129.6 (+),

128.4 (+), 128.4 (+), 123.8 (-), 118.4 (+), 62.01 (+), 39.6 (-), 26.3 (-), 25.7 (+), 17.81 (+),

16.67 (+); GC: Rt= 36.392 min, MS (EI), m/z (%): 292 (M+·, 34), 111 (100), 123 (59), 77

(53), 69 (98), 41 (44); HRMS (ESI+): m/z: calcd for C17H22ClO2 ([M+H]+) 293.1303,

found: 293.1299; calcd for C17H21ClNaO2 ([M+Na]+) 315.1122, found: 315.1126.

(E)-3,7-dimethylocta-2,6-dien-1-yl 2-hydroxybenzoate (12f): Yellow oil (0.23 g, 0.83

mmol, 38%), Rf: [hexane-EtOAc 15:1] = 0.45; IR(ATR, cm-1): 3210 (OH), 2918 (CH),

1671 (C=O), 1612 (C=C), 1210 (C-O), 723 (C=C-H); 1H NMR (400 MHz, CDCl3), δ(ppm):

10.71 (1H, s, OH), 8.40 (1H, dd, J = 3.3, 1.7 Hz, 6’-HAr), 7.88 (1H, td, J = 7.8, 1.7 Hz,

7’-HAr), 7.66 (1H, td, J = 7.7, 1.1 Hz, 5’-HAr), 7.51 (1H, dd, J = 8.1, 1.1 Hz, 3’-HAr),

5.49–5.45 (1H, m, 4-H), 5.37–5.32 (1H, m, 8-H), 5.00 (2H, d, J = 7.2 Hz, -CH2-), 2.33–

2.16 (4H, m, -CH2-), 1.98 (3H, s, 10-CH3), 1.89 (3H, s, 12-CH3), 1.87 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 164.5, 149.5, 142.7, 136.2 (+), 133.7 (+), 131.5,

130.6 (+), 126.4 (+), 123.7 (+), 119.4 (+), 62.1 (+), 39.3 (-), 26.1 (-), 25.6 (+), 17.6 (+),

16.2 (+); GC: Rt= 48.872 min, MS (EI), m/z (%): 274 (M+·, 21), 231 (67), 193 (53), 69

(100), 67 (20), 44 (28); HRMS (ESI+): m/z: calcd for C17H21O3 ([M-H]-) 273.1496,

found: 273.1498; calcd for C17H22NaO3 ([M+Na]+) 297.1461, found: 297.1466.

(E)-3,7-dimethylocta-2,6-dien-1-yl 4-hydroxy-3-methoxybenzoate (12g): Colorless oil,

(0.11 mg, 0.35 mmol, 40%), Rf [hexane-EtOAc 10:1]=0.2; IR (ATR, cm-1): 3314 (OH),

2967 (CH), 1710 (C=O), 1634 (C=C), 1280 (C-O), 877 (C=C-H); 1H NMR (400 MHz,

CDCl3), δ(ppm): 7.62 (1H, dd, J = 8.3, 1.9 Hz, 3’-HAr), 7.53 (1H, d, J = 1.9 Hz, 4’-HAr),

6.90 (1H, d, J = 8.3 Hz, 6’-HAr), 6.50 (1H, s, OH), 5.42–5.37 (1H, m, 4-H), 5.07 (1H,

ddd, J = 7.0, 4.0, 1.3 Hz, 8-H), 4.13 (2H, d, J = 6.9 Hz, -CH2-), 3.92 (3H, s, 8’-CH3),

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-5

2.08 (2H, dd, J = 16.1, 6.3 Hz, -CH2-), 2.03–1.99 (2H, m, -CH2-), 1.66-1.65 (6H, m, 10-

CH3, 12-CH3), 1.58 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 166.6, 150.1,

146.3 (+), 142.1 (+), 131.9, 124.2, 123.8 (+), 122.5 (+), 118.6 (+), 114.2 (+), 111.9 (+),

59.4 (-), 39.6 (-), 26.44 (-), 25.7 (+), 17.7 (+), 16.3 (+); GC: Rt= 53.971 min, MS (EI),

m/z (%): 342 (M+·, 23), 206 (32), 81 (44), 69 (100), 67 (28), 41 (56); HRMS (ESI+):

m/z: calcd for C18H23O4 ([M-H]-) 303.1602, found: 303.1598; calcd for C18H24NaO4

([M+Na]+) 327.1567 found: 327.1564.

(E)-3,7-dimethylocta-2,6-dien-1-yl nicotinate (12h): Yellow oil (0.17 g, 0.65 mmol,

84% yield) Rf: [hexane-EtOAc 15:1] = 0.30; IR(ATR, cm-1): 2920 (CH), 1719 (C=O),

1591 (C=C), 1274 (C-O), 740 (C=C-H); 1H NMR (400 MHz, CDCl3), δ(ppm): 9.21 (1H, dd,

J = 2.1, 0.7 Hz, 4’-HAr), 8.74 (1H, dd, J = 4.9, 1.7 Hz, 7’-HAr), 8.29–8.26 (1H, m, 3’-

HAr), 7.36 (1H, ddd, J = 8.0, 4.9, 0.8 Hz, 5’-HAr) 5.45 (1H, td, J = 7.2, 1.2 Hz, 4-H),

5.08–5.05 (1H, m, 8-H), 4.85 (d, J = 7.1 Hz, 2H, -CH2-), 2.14–2.03 (4H, m, -CH2-), 1.75

(3H, s, 12-CH3), 1.65 (3H, s, 10-CH3), 1.58 (3H, s, 11-CH3); 13C NMR (101 MHz,

CDCl3), δ(ppm): 165.2, 153.2 (+), 150.9 (+), 143.0, 137.0 (+), 131.8, 126.3, 123.6 (+),

123.2, (+), 117.9 (+), 62.2 (-), 39.5 (+), 26.2 (+), 25.6 (+), 17.6 (+), 16.5 (+); COSY

Correlation [δH/δH]: 9.21/8.28 [4’-HAr/3’-HAr], 8.74/7.36 [7’-HAr/5’-HAr], 8.28/7.36 [3’-

HAr/5’-HAr], 7.36/8.29–8.26 [5’-HAr/3’-HAr], 5.45/4.85/2.14–2.03/1.75.[4-H/-CH2-/-CH2-

/11-CH3], 5.08–5.05/1.65/2.14–2.03 [8-H/10-CH3/-CH2-], 4.85/5.45/2.14-2.03/1.75/ [-

CH2-/4-H/-CH2-/12-CH3], 2.14–2.03/5.08–5.05/ [-CH2-/8-H], 1.75/5.45 [12-CH3/4-H],

1.65/5.08–5.05 [10-CH3/8-H], 1.58/5.08–5.05[11-CH3/8-H]; HSQC Correlation [δH/δC]:

9.21/150.9 [4’-H/4’-C], 8.74/153.2 [7’-H/7’-C], 8.28/137.0 [3’-HAr/3’-C], 7.36/123.3

[5’-HAr/5’-C], 5.45/117.9 [4-H/4-C], 5.08-5.05/123.6 [8-H/8-C], 4.85/62.2 [-CH2-/3-C],

2.03-2.14/39.5 [-CH2-/6-C], 2.03-2.14/26.2 [-CH2-/7-C], 1.75/16.5 [12-CH3/12-C],

1.65/25.6 [10-CH3/10-C], 1.58/17.67 [11-CH3/11-C]; HMBC Correlation [δH/δC]:

9.21/126.3/137.0/150.9/153.2/165.2 [4’-HAr/2’-C/3’-C/4’-C/7’-C/1-C], 8.74/123.2/137.0

/150.7 [7’-HAr/5’-C/3’-C/4’C], 8.28/150.9/153.2/165.2 [3’-HAr/4’-C/7´-C/1-C], 7.36/

126.3/153.2 [5’-HAr/2’-C/7’-C], 5.45/16.5/39.3/62.2 [4-H/12-C/6-C/3-C], 5.06/17.6/

25.6/39.5 [8-H/10-C/11-C/6-C], 4.85/117.9/143.0/165.2 [-CH2-/4-C/5-C/1-C], 2.03-

2.14/16.5/25.6/39.4/ 117.9/123.6/131.8/143.0 [-CH2-,-CH2-/12-C/10-C/6-C/4-C/8-C/9-

C/5-C], 1.75/17.6/39.5/117.9/143.0 [12-CH3/11-C/6-C/4-C/5-C], 1.65/17.6/39.5/123.6

/131.8 [10-CH3/11-C/6-C/8-C/9-C], 1.58/25.6/123.6/131.8 [11-CH3/10-C/8-C/9-C].GC:

Rt= 22.810 min, MS (EI), m/z (%): 259 (M+·, 35), 124 (100), 106 (50), 78 (37), 69 (98),

41 (80); HRMS (ESI+): m/z: calcd for C16H22NO2 ([M+H]+) 260.1645, found: 260.1647;

calcd for C16H21KNO2 ([M+K]+) 298.1204, found: 298.1207.

(E)-3,7-dimethylocta-2,6-dien-1-yl-2-phenylacetate (12i): Colorless oil (0.26 g, 0.97

mmol, 80%), Rf [hexane-EtOAc 15:1] = 0.7; IR (ATR, cm-1): 2922 (CH), 1732 (C=O),

1602 (C=C), 1114 (C-O), 699 (C=C-H); 1H NMR (400 MHz, CDCl3), δ(ppm): 7.35–7.23

(5H, m, 4’-HAr, 5’-HAr, 6’-HAr, 7’-HAr, 8’-HAr), 5.34 (1H, td, J = 7.1, 0.9 Hz, 4-H), 5.07

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-6

(1H, ddd, J = 6.9, 4.0, 1.3 Hz, 8-H), 4.61 (2H, d, J = 7.1 Hz, -CH2-), 3.62 (2H, s, -CH2-),

2.12–2.01 (4H, m, -CH2-), 1.68 (6H, s, 10-CH3, 12-CH3), 1.60 (3H, s, 11-CH3); 13C

NMR (101 MHz, CDCl3), δ(ppm): δ 171.7, 142.4, 134.1 (+), 131.8, 129.3 (+), 128.5 (+),

127.0 (+), 123.7 (+), 118.1 (+), 61.8 (-), 41.4 (-), 39.5 (-), 26.2 (-), 25.7 (+), 17.7 (+),

16.5 (+); GC: Rt= 22.827 min, MS (EI), m/z (%): 272 (M+·, 30), 191 (86), 93 (32), 69

(100), 68 (40), 41 (54); HRMS (ESI+): m/z: calcd for C18H25O2 ([M+H]+) 273.1849,

found: 273.1853; calcd for C18H24KO2 ([M+K]+) 311.1408, found: 311.1411.

(±)-(E)-3,7-dimethylocta-2,6-dien-1-yl 2-hydroxy-2-phenylacetate (12j): Yellow oil

(0.19 g, 0.66 mmol, 28%), Rf: [hexane-EtOAc 15:1] = 0.5; IR(ATR, cm-1): 3346 (OH),

2918 (CH), 1746 (C=O), 1669 (C=C), 1240 (C-O), 831 (C=C-H); 1H NMR (400 MHz,

CDCl3), δ(ppm): 7.40–7.19 (5H, m, 3’-HAr, 4’-HAr, 5’-HAr, 6’-HAr, 7’-HAr), 5.89 (1H, s, 2’-

H), 5.38–5.33 (1H, m, 4-H), 5.08–5.03 (1H, m, 8-H), 4.08 (2H, dd, J = 6.8, 0.5 Hz, -

CH2-), 2.70 (1H, s, OH), 2.09-1.94 (4H, m, -CH2-), 1.64 (3H, s, 10-CH3), 1.62 (3H, s,

12-CH3), 1.56 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 164.1, 138.8, 133.7,

131.4, 129.3 (+), 128.4 (+), 127.2 (+), 123.9 (+), 74.7 (+), 58.9 (-), 39.4 (-), 26.3 (-),

25.5 (+), 17.5 (+), 16.1 (+); GC: Rt= 42.332 min, MS (EI), m/z (%): 288 (M+·, 42), 271

(100), 107 (36), 77 (69), 69 (89), 41 (38); HRMS (ESI+): m/z: calcd for C18H23O3 ([M-

H]-) 287.1653, found: 287.1650; calcd for C18H28NO3 ([M+NH4]+) 306.2064, found:

306.2067.

(E)-3,7-dimethylocta-2,6-dien-1-yl-3-phenylpropanoate (12k): Colorless oil, (0.141 g,

0.492 mmol, 71%), Rf [hexane-EtOAc 15:1] =0.5; IR (ATR, cm-1): 2922 (CH), 1732

(C=O), 1602 (C=C), 1155 (C-O), 699 (C=C-H) ; 1H NMR (400 MHz, CDCl3), δ(ppm): 7.33–

7.28 (2H, m, 5’-HAr, 6’-HAr), 7.24–7.19 (3H, m, 7’-HAr, 8’-HAr, 9’-HAr), 5.37–5.33 (1H,

m, 4-H), 5.11 (1H, ddd, J = 6.9, 4.1, 1.3 Hz, 8-H), 4.63 (2H, d, J = 7.1 Hz, 3-H), 3.01–

2.96 (2H, m, -CH2-), 2.68–2.63 (2H, m, -CH2-), 2.16–2.05 (4H, m, -CH2-), 1.72 (6H, s,

10-CH3, 12-CH3), 1.63 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 172.9,

142.2, 140.6 (+), 131.8, 128.5 (+), 128.3 (+), 126.2, 123.8 (+), 118.3 (+), 61.4 (-), 39.5 (-

), 35.9 (-), 31.0 (-), 26.3 (-), 25.7 (+), 17.7 (+), 16.5 (+); GC: Rt= 38.897 min, MS (EI),

m/z (%): 286 (M+·, 34), 217 (74), 91 (100), 69 (88), 67 (44); HRMS (ESI+): m/z: calcd

for C19H27O2 ([M+H]+) 287.2006, found: 287.2009; calcd for C19H26NaO2 ([M+Na]+)

309.1825, found: 309.1821.

(E)-3,7-dimethylocta-2,6-dien-1-yl-3-(4-methoxyiphenyl)propanoate (12l): Colorless

oil (0.137 g, 0.432 mmol, 68%), Rf [hexane-EtOAc 15:1] = 0.4; IR (ATR, cm-1): 2915

(CH), 1731 (C=O), 1613 (C=C), 1245 (C-O), 825 (C=C-H); 1H NMR (400 MHz, CDCl3),

δ(ppm): 7.14–7.10 (2H, m, 7’-HAr, 8’-HAr), 6.84–6.81 (2H, m, 5’-HAr, 6’-HAr), 5.32 (1H,

ddd, J = 7.1, 2.4, 1.2 Hz, 4-H), 5.09 (1H, ddd, J =6.9, 4.1, 1.3 Hz, 8-H), 4.59 (2H, d, J =

7.1 Hz, -CH2-), 3.78 (3H, s, 10’-CH3), 2.90 (2H, t, J = 7.8 Hz, -CH2-), 2.62–2.58 (2H, m,

-CH2-), 2.13–2.02 (4H, m, -CH2-), 1.69 (6H, s, 10-CH3, 12-CH3), 1.61 (3H, s, 11-CH3);

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García, Puerto & Kouznetsov ESI-7

13C NMR (101 MHz, CDCl3), δ(ppm): 173.1, 158.0 (+), 142.3, 132.7, 131.9, 129.3 (+),

123.8 (s, 8-H), 118.3 (+), 113.9 (+), 61.4 (-), 55.2 (+), 39.6 (-), 36.3 (-), 30.2 (-), 26.3 (-),

25.8 (+), 17.8 (+), 16.5 (+); GC: Rt= 20.89 min, MS (EI), m/z (%): 316 (M+·, 33), 179

(46), 137 (58), 121 (100), 93 (30), 69 (72); HRMS (ESI+): m/z: calcd for C20H29O3

([M+H]+) 317.2111, found: 317.2115; calcd for C20H32NO3 ([M+NH4]+) 334.2377,

found: 334.2374.

(E)-3,7-dimethylocta-2,6-dien-1-yl-cinamate (12m): Colorless oil (0.167 g, 0.587

mmol, 90% yield) Rf: [hexane-EtOAc 15:1] = 0.5; IR (ATR, cm-1): 2926 (CH), 1709

(C=O), 1636 (C=C), 1162 (C-O), 767 (C=C-H); 1H NMR (400 MHz, CDCl3), δ(ppm): 7.70

(1H, d, J = 16.0 Hz, -CH-), 7.54-7.49 (2H, m, 5’-HAr, 6’-HAr), 7.41–7.35 (3H, m, 7’-HAr,

8’-HAr, 9’-HAr), 6.46 (1H, d, J = 16.0 Hz, -CH-), 5.45–5.41 (1H, m, 4-H), 5.12–5.08

(1H, m, 8-H), 4.74 (2H, d, J = 7.1 Hz, -CH2-), 2.16–2.05 (4H, m, -CH2-), 1.75 (3H, d, J

= 1.1 Hz, 12-CH3), 1.69 (3H, d, J = 1.0 Hz, 10-CH3), 1.61 (3H, s, 11-CH3); 13C NMR

(101 MHz, CDCl3), δ(ppm): 167.1, 144.7 (+), 142.5 (+), 134.5, 131.9, 128.9 (+), 128.1

(+), 123.8 (+), 118.3 (+), 118.2 (+), 61.5 (-), 39.6 (-), 26.3 (-), 25.8 (+), 17.8 (+), 16.6

(+); GC: Rt= 26.069 min, MS (EI), m/z (%): 284 (M+·, 38), 131 (100), 103 (40), 93 (52),

69 (57), 41 (32); HRMS (ESI+): m/z: calcd for C19H25O2 ([M+H]+) 285.1849, found:

285.1853; calcd for C19H24NaO2 ([M+Na]+) 307.1669, found: 307.1665.

(E)-3,7-dimethylocta-2,6-dien-1-yl (E)-3-(4-hydroxy-3-methoxyphenyl)acrylate (12n):

Colorless oil (2.02 mg, 0.605 mmol, 10%), Rf [hexane-EtOAc 4:1] = 0.4; IR (ATR, cm-

1): 3347 (OH), 2918 (CH), 1692 (C=O), 1631 (C=C), 1158 (C-O), 817 (C=C-H); 1H NMR

(400 MHz, CDCl3), δ(ppm): 7.62 (1H, d, J = 15.9 Hz, -CH-), 7.06 (1H, dd, J = 8.2, 1.8 Hz,

5’-HAr), 7.02 (1H, d, JHH= 1.9 Hz, 7’-HAr), 6.91 (1H, d, J = 8.1 Hz, 6’-HAr), 6.30 (1H, d,

J = 15.9 Hz, -CH2-), 5.92 (1H, s, OH), 5.42 (1H, td, J = 7.1, 1.2 Hz, 4-H), 5.09 (1H, ddd,

J = 6.8, 4.1, 1.3 Hz, 8-H), 4.72 (2H, d, J = 7.2 Hz, -CH2-), 3.91 (3H, s, 10’-CH3), 2.15–

2.04 (4H, m, -CH2-), 1.74 (3H, s, 12-CH3), 1.68 (3H, s, 10-CH3), 1.60 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): δ 167.5, 147.9, 146.8 (+), 144.9 (-), 142.5, 132.0,

127.2, 123.8 (+), 123.2 (+), 118.4 (+), 115.6 (-), 114.8, 109.2 (+), 61.4 (-), 56.0 (+), 39.7

(-), 26.4 (-), 25.8 (+), 17.8 (+), 16.6 (+); GC: Rt= 50.875 min, MS (EI), m/z (%): 330

(M+·, 31), 206 (32), 149 (100), 81 (44), 69 (80), 44 (32); HRMS (ESI+): m/z: calcd for

C20H27O4 ([M+H]+) 331.1904, found: 331.1907; calcd for C20H26NaO4 ([M+Na]+)

353.1723, found: 353.1726.

(E)-3,7-dimethylocta-2,6-dien-1-yl-(3,4-dimethoxy)cinnamate (12o): Colorless oil

(89.2 mg, 0.25 mmol, 54%), Rf: [hexane-EtOAc 10:1] = 0.6; IR (ATR, cm-1): 2967

(CH), 1706 (C=O), 1634 (C=C), 1257 (C-O), 732 (C=C-H); 1H NMR (400 MHz, CDCl3),

δ(ppm): 7.62 (1H, d, J = 15.9 Hz, -CH2-), 7.08 (1H, dd, J = 8.3, 1.9 Hz, 6’-HAr), 7.03 (1H,

d, J = 1.9 Hz, 8’-HAr), 6.84 (1H, d, J = 8.3 Hz, 5’-HAr), 6.32 (1H, d, JHH= 15.9 Hz, -CH2-

), 5.43–5.38 (m, 4-H), 5.08 (1H, td, J = 5.6, 2.9 Hz, 8-H), 4.71 (2H, d, J = 7.1 Hz, -CH2-

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García, Puerto & Kouznetsov ESI-8

), 3.89 (6H, d, J = 2.3 Hz, 10’-CH3, 11’-CH3), 2.15–1.98 (4H, m, -CH2-), 1.73 (3H, s,

12-CH3), 1.67 (3H, s, 10-CH3), 1.59 (s, 3H, 11-CH3); 13C NMR (101 MHz, CDCl3),

δ(ppm): 167.3, 151.0, 149.1, 144.6, 142.4 (+), 131.9, 127.4, 123.3 (+), 122.7 (+), 118.4

(+), 115.9 (+), 111.0 (+), 109.4, 61.4 (-), 55.9 (+), 39.6 (-), 26.3 (-), 25.7 (+), 17.7 (+),

16.6 (+); GC: Rt= 21.159 min, MS (EI), m/z (%): 334 (M+·, 18), 241 (70), 153 (18), 69

(100), 68 (23), 67 (22); HRMS (ESI+): m/z: calcd for C21H29O4 ([M+H]+) 345.2060,

found: 345.2064; calcd for C21H28NaO4 ([M+Na]+) 367.1880, found: 367.1876.

(E)-3,7-dimethylocta-2,6-dien-1-yl-(3,4,5-trimethoxy)cinnamate (12p): Colorless oil

(24.0 mg, 0.629 mmol, 47 %), Rf [hexane-EtOAc 15:1] = 0.3; IR (ATR, cm-1): 2926

(CH), 1707 (C=O), 1636 (C=C), 1272 (C-O), 826 (C=C-H); 1H NMR (400 MHz, CDCl3),

δ(ppm): 7.59 (1H, d, JHH= 15.9 Hz, -CH2-), 6.74 (2H, s, 5’-HAr, 6’-HAr), 6.35 (1H, d, JHH=

15.9 Hz, -CH2-), 5.43–5.38 (1H. m, 4-H), 5.10–5.06 (1H, m, 8-H), 4.72 (2H, d, J = 7.1

Hz, -CH2-), 3.86 (m, 10’-CH3, 11’-CH3, 12’-CH3), 2.14–1.99 (4H, m, -CH2-), 1.74 (3H,

s, 12-CH3), 1.67 (3H, s, 10-CH3), 1.59 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3),

δ(ppm): 167.0, 153.5, 144.7 (+), 142.6, 131.9, 117.9 (+), 105.3 (+), 61.5 (-), 56.2 (+), 39.6

(-), 26.4 (-), 25.7 (+), 16.62 (+), 16.35 (+); GC: Rt= 37.930 min, MS (EI), m/z (%): 374

(M+·, 25), 238 (100), 223 (54), 221 (69), 169 (49), 41 (49); HRMS (ESI+): m/z: calcd for

C22H31O5 ([M+H]+) 375.2166, found: 375.2162; calcd for C22H30NaO5 ([M+Na]+)

397.1985, found: 397.1988.

3. Characterization data of all synthesized 6,7-epoxy geranyl esters 13a-13k

(E)-3,7-dimethylocta-2-en, 6,7-epoxy-1-yl acetate (13a): Colorless oil (46.0 mg, 0.22

mmol, 35% yield); Rf [hexane-EtOAc 15:1] = 0.4; IR (ATR, cm-1): 2963 (CH), 1735

(C=O), 1616 (C=C), 1230 (C-O), 1022 (C-O epox), 870 (C=C-H); 1H NMR (400 MHz,

CDCl3), δ(ppm): 5.37-5.33 (1H, m, 4-H), 4.56 (2H, d, J = 7.1 Hz, -CH2-), 2.67 (1H, t, J =

6.2 Hz, 8-H), 2.17 (2H, qd, J = 14.4, 7.2 Hz, -CH2-), 2.02 (3H, s, 2’-CH3), 1.69 (3H, s,

12-CH3), 1.66–1.60 (2H, m, -CH2-), 1.27 (3H, s, 10-CH3), 1.23 (3H, s, 11-CH3); 13C

NMR (101 MHz, CDCl3), δ(ppm): 171.1, 141.3, 118.8 (+), 63.9 (+), 61.3 (-), 58.5, 36.2 (-

), 27.0 (-), 24.9 (+), 21.1 (+), 18.8 (+), 16.5 (+). GC: Rt= 24.237 min, MS (EI), m/z (%):

212 (M+·, 53), 193 (18), 69 (100), 68 (23), 67 (22), 41 (70); HRMS (ESI+): m/z: calcd

for C12H21O3 ([M+H]+) 213.1485, found: 213.1488; calcd for C12H20NaO3 ([M+Na]+)

235.1305, found: 235.1309.

(±)-(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-5-(1,2-dithiolan-3-yl)pentanoate (13b):

Yellow oil (238.0 mg, 0.639 mmol, 30% yield); Rf [hexane-EtOAc 15:1] = 0.3; IR

(ATR, cm-1): 2928 (CH), 1726 (C=O), 1262 (C-O), 1075 (C-O epox), 732 (C=C-H); 1H

NMR (400 MHz, CDCl3), δ(ppm): δ 5.35–5.30 (1H, m, 4-H), 4.59 (2H d, J = 7.1 Hz, -

CH2-), 3.59 (1H, m, 6’-H), 3.36–3.25 (2H, m, -CH2-), 3.08–2.98 (1H m, 8-H), 2.37–2.30

(2H m, -CH2-), 2.13–2.00 (4H, m, -CH2-), 1.91–1.80 (2H, m, -CH2-), 1.70 (3H, s, 12-

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García, Puerto & Kouznetsov ESI-9

CH3), 1.68 (1H, s, 10-CH3), 1.66–1.61 (4H, m, -CH2-), 1.60 (1H, s, 10-CH3), 1.49–1.40

(1H, m, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): δ 173.3, 142.6, 118.2 (+), 75.4

(+), 61.5 (-), 59.7, 55.3 (+), 39.6 (-), 36.7 (-), 36.3 (-), 34.0 (-), 33.9 (-), 28.2 (-), 26.4 (-),

25.8 (+), 24.8 (-), 17.8 (+), 16.6 (+); GC: Rt= 23.511 min, MS (EI), m/z (%): 358 (M+·,

46), 285 (100), 159 (73), 73 (69), 43 (40); HRMS (ESI+): m/z: calcd for C18H31O3S2

([M+H]+) 359.1709, found: 359.1712; calcd for C18H30NaO3S2 ([M+Na]+) 381.1529,

found: 381.1526.

(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-benzoate (13c): Colorless oil (0.106 g, 0.968

mmol, 40%), Rf: [hexane-EtOAc 15:1] = 0.3; IR (ATR, cm-1): 2962 (CH), 1715 (C=O),

1601 (C=C), 1268 (C-O), 1107 (C-O epox), 710 (C=C-H); 1H NMR (400 MHz, CDCl3),

δ(ppm): 8.04 (2H, dt, J = 8.5, 1.8 Hz, 3’-HAr, 4’-HAr), 7.56–7.52 (1H, m, 7’-HAr), 7.44–

7.40 (2H, m, 5’-HAr, 6’-HAr), 5.51 (1H, td, J = 7.0, 1.2 Hz, 4-H), 4.84 (2H, d, J = 7.0 Hz,

-CH2-), 2.71 (1H, t, J = 6.3 Hz, 8-H), 2.29–2.13 (2H, m, -CH2-), 1.78 (3H, s, 12-CH3),

1.73–1.65 (2H, m, -CH2-), 1.29 (3H, s, 10-CH3), 1.26 (3H, s, 11-CH3); 13C NMR (101

MHz, CDCl3), δ(ppm): 166.7, 141.5, 132.9 (+), 130.4, 129.6 (+), 128.4 (+), 119.1 (+), 64.0

(+), 61.8 (-), 58.6, 36.3 (-), 27.1 (-), 24.9 (+), 18.8 (+), 16.6 (+); COSY Correlation

[δH/δH]: 8.04/7.44–7.40 [7’-HAr/5’-HAr, 6’-HAr], 5.51/4.84/1.78 [4-H/3-CH2-/12-CH3],

4.84/1.78 [3-CH2-/12-CH3], 2.71/1.73–1.65 [8-H/7-CH2-], 2.29–2.13/1.73–1.65 [6-CH2-

/7-CH2-]; HSQC Correlation [δH/δC]: 8.04/129.6 [3’-HAr, 4’-HAr/3’-C, 4’-C], 7.56–

7.52/132.9 [7’-HAr/7’C], 7.44–7.40/128.4 [5’-HAr, 6’-HAr/5’-C, 6’-C], 5.51/119.1 [4-

H/4-C], 4.84/61.8 [-CH2-/3-C], 2.71/64.0 [8-H/8-C], 2.29–2.13/36.3 [-CH2-/6-C],

1.78/16.6 [12-CH3/12-C], 1.73–1.65/27.1 [-CH2-/7-C], 1.29/24.9 [12-CH3/12-C],

1.26/18.8 [10-CH3/10-C]; HMBC Correlation [δH/δC]: 8.04/129.6/132.9/166.7 [3’-HAr,

4’-HAr/3’-C, 4’-C/7’-C/1-C], 7.54/129.6 [7’-HAr/3’-C, 4’-C], 7.44–7.40/128.4 [5’-HAr,

6’-HAr/5’-C, 6’-C], 5.51/16.6/36.3 [4-H/12-C/6-C], 4.84/119.1/141.5/166.7 [-CH2-/4-

C/5-C/1-C], 2.71/27.1 [-CH2-/7-C], 2.29–2.13/16.6/27.1/64.0/119.1/141.5 [-CH2-/12-

C/7-C/8-C/4-C/5-C], 1.78/36.3/119.1/141.4 [12-CH3/6-C/4-C/5-C], 1.73–1.65/36.3/64.0

/141.5 [-CH2-/6-C/8-C/5-C].GC: Rt= 18.235 min, MS (EI), m/z (%): 274 (M+·, 51), 219

(36), 105 (100), 79 (42), 76 (30), 85 (24); HRMS (ESI+): m/z: calcd for C17H23O3

([M+H]+) 275.1642, found: 275.1645; calcd for C17H22NaO3 ([M+Na]+) 297.1461,

found: 297.1464.

(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl nicotinate (13d): Red oil, 0.140 g, 0.508

mmol, 62% yield) Rf: [hexane-OEtAc 15:1] = 0.4; IR (ATR, cm-1): 2961 (CH), 1719

(C=O), 1590 (C=C), 1274 (C-O), 1108 (C-O epox), 871 (C-O epox asym. flex.), 826 (C=C-H); 1H

NMR (400 MHz, CDCl3), δ(ppm): 9.21 1H, (dd, J = 2.2, 0.8 Hz, 4’-HAr), 8.76 (1H, dd, J =

4.9, 1.7 Hz, 7’-HAr), 8.29 (1H, dt, J = 8.0, 2.0 Hz, 3’-HAr), 7.38 (1H, ddd, J = 8.0, 4.9,

0.9 Hz, 5’-HAr), 5.53–5.48 (1H, m, 4-H), 4.87 (2H, d, J = 7.1 Hz, -CH2-), 2.71 (1H, t, J =

6.2 Hz, 8-H), 2.30–2.14 (2H, m, -CH2-), 1.79 (3H, s, 12-CH3), 1.68 (2H, td, J = 7.8, 6.3

Hz, -CH2-), 1.29 (3H, s, 10-CH3), 1.26 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3),

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García, Puerto & Kouznetsov ESI-10

δ(ppm): 165.4, 153.4 (+), 151.0 (+), 142.2, 137.2 (+), 126.3, 123.4 (+), 118.5 (+), 64.0 (+),

62.2 (-), 58.5, 36.3 (-), 27.1 (-), 24.9 (+), 18.8 (+), 16.7 (+); GC: Rt= 41.448 min, MS

(EI), m/z (%): 275 (M+·, 49), 206 (100), 124 (67), 79 (51), 78 (44), 85 (35); HRMS

(ESI+): m/z: calcd for C16H22NO3 ([M+H]+) 276.1594, found: 276.1598; calcd for

C16H21NNaO3 ([M+Na]+) 298.1414, found: 298.1410.

(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl 2-chlorobenzoate (13e): Pale pink oil (98.0

mg, 0.32 mmol, 79 % yield); Rf [hexane-OEtAc 15:1] = 0.2; IR (ATR, cm-1): 2962

(CH), 1726 (C=O), 1592 (C=C), 1246 (C-O), 748 (C=C-H); 1H NMR (400 MHz, CDCl3),

δ(ppm): 7.81 (1H, dd, J = 7.8, 1.6 Hz, 4’-HAr), 7.42 (2H, dtd, J = 9.7, 7.9, 1.5 Hz, 6’-HAr,

7’-HAr), 7.30 (1H, ddd, J = 8.7, 5.4, J = 1.6 Hz, 5’-HAr), 5.53 (1H, td, J = 7.1, 1.2 Hz, 4-

H), 4.87 (2H, d, J = 7.2 Hz, -CH2-), 2.73 (1H, t, J = 6.2 Hz, 8-H), 2.31–2.15 (2H, m, -

CH2-), 1.80 (3H, s, 12-CH3), 1.69 (2H, dt, J = 13.9, 7.0 Hz, -CH2-), 1.30 (3H, s, 11-

CH3), 1.27 (1H, s, 10-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 165.8, 142.0, 133.6

(+), 132.5, 131.4 (+), 131.0, 130.3 (+), 126.6 (+), 118.6 (+), 63.9 (+), 62.3 (-), 58.5, 36.2

(-), 27.1 (-), 24.9 (+), 18.83 (+), 16.68 (+); GC: Rt= 22.445 min, MS (EI), m/z (%): 308

(M+·, 50), 209 (28), 169 (38), 111 (51), 105 (88), 85 (100); HRMS (ESI+): m/z: calcd for

C17H22ClO3 ([M+H]+) 309.1252, found: 309.1255; calcd for C17H21ClNaO3 ([M+Na]+)

331.1071, found: 331.1068.

(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-2-phenylacetate (13f): Colorless oil (40.0

mg, 0.138 mmol, 20% yield); ); Rf [hexane-OEtAc 15:1] = 0.3; IR (ATR, cm-1): 2967

(CH), 1733 (C=O), 1594 (C=C), 1248 (C-O), 727 (C=C-H); 1H NMR (400 MHz, CDCl3),

δ(ppm): 7.34–7.24 (5H, m, 4’-HAr, 5’-HAr, 6’-HAr, 7’-HAr, 8’-HAr), 5.53–5.48 (1H, m,4-H),

4.60 (2H, d, J = 7.1 Hz, -CH2-), 3.61 (2H, s, -CH2-), 2.70 (2H, dd, J = 13.7, 6.4 Hz, 8-

H), 2.30–2.09 (2H, m,-CH2-), 1.79 (3H, s, 12-CH3), 1.67-1.60 (2H, m, -CH2-), 1.29 (6H,

s, 11-CH3, 10-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 171.7, 141.5, 135.0, 129.3 (+),

128.9 (+), 127.1 (+), 118.8 (+), 64.0 (+), 61.7 (-), 58.5, 41.4 (+), 36.3 (-), 27.0 (-), 24.9

(+), 18.8 (+), 16.7 (+); GC: Rt= 19.215 min, MS (EI), m/z (%): 288 (M+·, 59), 208 (64),

191 (100), 116 (26), 71 (26); HRMS (ESI+): m/z: calcd for C18H25O3 ([M+H]+)

289.1798, found: 289.1801; calcd for C18H24NaO3 ([M+Na]+) 311.1618, found:

311.1621.

(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-3-phenylpropanoate (13g): Colorless oil

(85.0 mg, 0.281 mmol, 70% yield), Rf [hexane-OEtAc 10:1] = 0.5; IR (ATR, cm-1): 2960

(CH), 1731 (C=O), 1245 (C-O), 1078 (C-O epox), 872 (C=C-H); 1H NMR (400 MHz,

CDCl3), δ(ppm): 7.28 (2H, t, J = 5.2 Hz, 5’-HAr, 6’-HAr), 7.21–7.17 (3H, m, 7’-HAr, 8’-

HAr, 9’-HAr), 5.35 (1H, td, J = 7.1, 1.2 Hz, 4-H), 4.59 (2H, d, J = 7.1 Hz, -CH2-), 2.95

(2H, t, J = 7.9 Hz, -CH2-), 2.70 (1H, t, J = 6.2 Hz, 8-H), 2.65–2.60 (2H, m, -CH2-),

2.26–2.10 (2H, m, -CH2), 1.71 (3H, s, 12-CH3), 1.65 (2H, td, J = 7.9, 3.7 Hz, -CH2-),

1.30 (3H, s, 10-CH3), 1.26 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 173.0,

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García, Puerto & Kouznetsov ESI-11

141.3, 140.6, 128.5 (+), 128.3 (+), 118.9 (+), 64.0 (+), 61.3 (-), 58.5, 36.2 (-), 36.0 (-),

31.0 (-), 27.1 (-), 24.9 (+), 18.8 (+), 16.5 (+); GC: Rt= 19.748 min, MS (EI), m/z (%):

302 (M+·, 47), 225 (100), 133 (36), 91 (96), 81 (70), 71 (80); HRMS (ESI+): m/z: calcd

for C19H27O3 ([M+H]+) 303.1955, found: 303.1958; calcd for C19H26NaO3 ([M+Na]+)

325.1774, found: 325.1773.

(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-3-(4-methoxyphenyl)propanoate (13h):

Colorless oil (56.1 mg, 0.16 mmol, 81% yield); Rf (Hexane:AcOEt 10:1)=0.3 IR (ATR,

cm-1): 2959 (CH), 1730 (C=O), 1612 (C=C), 1244 (C-O), 1109 (C-O epox), 826 (C=C-H); 1H NMR (400 MHz, CDCl3), δ(ppm): 7.12-7.08 (1H, m, 7’-HAr, 8’-HAr), 6.83–6.79 (1H,

m, 5’-HAr, 6’-HAr), 5.37–5.32 (1H, m, 4-H), 4.58 (2H, d, J = 7.1 Hz, -CH2-), 3.77 (3H, s,

10’-CH3), 2.88 (2H, t, J = 7.8 Hz, -CH2-), 2.69 (1H, t, J = 6.3 Hz, 8-H), 2.60–2.56 (2H,

m, -CH2-), 2.25–2.09 (2H, m, -CH2-), 1.70 (3H, s, 12-CH3), 1.68–1.62 (1H, m, -CH2-),

1.29 (3H, s, 10-CH3), 1.25 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 173.0,

158.0 (+), 141.3 (+), 132.6, 129.3 (+), 118.9 (+), 113.9 (+), 64.0 (+), 61.2 (-), 58.5, 55.3

(+), 36.3 (-), 36.2 (-), 30.1 (-), 27.1 (-), 24.9 (+), 18.8 (+), 16.5 (+); GC: Rt= 21.867 min,

MS (EI), m/z (%): 332 (M+·, 44), 321 (89), 237 (100), 179 (48), 81 (48), 71 (60); HRMS

(ESI+): m/z: calcd for C20H29O4 ([M+H]+) 333.2060, found: 333.2063; calcd for

C20H28NaO4 ([M+Na]+) 355.1880, found: 355.18884.

(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-cinamate (13i): Colorless oil (0.140 g, 0.50

mmol, 40%), Rf: [hexane-OEtAc 15:1] = 0.3; IR (ATR, cm-1): 2962 (CH), 1709 (C=O),

1636 (C=C), 1162 (C-O), 1101 (C-O epox), 767 (C=C-H); 1H NMR (400 MHz, CDCl3),

δ(ppm): 7.68 (1H, d, J = 16.0 Hz, 2’-H), 7.54–7.48 (2H, m, 5’-HAr, 6’-HAr), 7.36 (3H, dd,

J = 6.7, 3.7 Hz, 7’-HAr, 8’-HAr, 9’-HAr), 6.43 (1H, d, J = 16.0 Hz, 3’-H), 5.45 (1H, td, J =

7.1, 1.3 Hz, 4-H), 4.72 (2H, d, J = 7.1 Hz, 3-H), 2.71 (1H, t, J = 6.3 Hz, 8-H), 2.28–2.12

(2H, m, -CH2-), 1.76 (3H, s, 12-CH3), 1.70–1.64 (2H, m, -CH2-), 1.30 (3H, s, 10-CH3),

1.26 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 167.0, 144.8 (+), 141.4,

128.9 (+), 128.1 (+), 119.0 (+), 118.1 (+), 64.0 (+), 61.4 (-), 58.5, 36.2 (-), 27.1 (-), 24.9

(+), 18.8 (+), 16.2 (+); GC: Rt= 44.189 min, MS (EI), m/z (%): 300 (M+·, 38), 231 (100),

103 (46), 93 (48), 69 (63), 41 (38); HRMS (ESI+): m/z: calcd for C19H25O3 ([M+H]+)

301.1798, found: 301.1795; calcd for C19H24NaO3 ([M+Na]+) 323.1618, found:

323.1616.

(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-(3,4-dimethoxy)cinnamate (13j): Colorless

oil (18.0 mg, 0.49 mmol, 42% yield), Rf [hexane-OEtAc 10:1] = 0.3; IR (ATR, cm-1):

2926 (CH), 1707 (C=O), 1636 (C=C), 1272 (C-O), 826 (C=C-H); 1H NMR (400 MHz,

CDCl3), δ(ppm): 7.62 (1H, d, J = 15.1 Hz, 2’-H), 7.26-7.24 (2H, m, 6’-HAr, 8’-HAr), 7.06

(1H, d, J = 7.7 Hz, 5’-HAr), 6.62 (1H, d, J = 15.1 Hz, 3’-HAr), 5.43-5.36 (1H, m, 4-H),

4.82 (2H, d, J = 7.1 Hz, -CH2-), 3.84 (3H, s, 10’-CH3), 3.76 (3H, s, 11’-CH3), 2.23 (1H,

t, J = 6.0 Hz, 8-H), 2.06–2.01 (2H, m, -CH2-), 1.77 (3H, s, 12-CH3), 1.64–1.54 (2H, m, -

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-12

CH2-), 1.32 (3H, s, -CH2-), 1.19 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm):

167.0, 153.4 (+), 144.8 (+), 141.6, 130.0, 118.9 (+), 117.4 (+), 105.1 (+), 64.0 (+), 61.4

(-), 58.5, 56.1 (+), 36.3 (-), 27.1 (-), 24.9 (+), 18.8 (+), 16.6 (+); GC: Rt= 23.511 min,

MS (EI), m/z (%): 360 (M+·, 52), 241 (100), 209 (80), 167 (77), 69 (68) 43 (76); HRMS

(ESI+): m/z: calcd for C21H29O5 ([M+H]+) 361.2010, found: 361.2007; calcd for

C21H28NaO5 ([M+Na]+) 383.1829, found: 383.1832.

(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-(3,4,5-trimethoxy)cinnamate (13k):

Colorless oil (0.104 g, 0.26 mmol, 42% yield), Rf [hexane-OEtAc 10:1] = 0.3; IR (ATR,

cm-1): 2962 (CH), 1707 (C=O), 1635 (C=C), 1273 (C-O), 1001 (C-O epox), 729 (C=C-H); 1H NMR (400 MHz, CDCl3), δ(ppm): 7.59 (1H, d, J = 15.9 Hz, 2’-H), 6.73 (2H, s, 5’-HAr,

6’-HAr), 6.34 (1H, d, J = 15.9 Hz, 3’-HAr), 5.48–5.43 (1H, m, 4-H), 4.72 (2H, d, J = 7.1

Hz, 3-H), 3.87 (6-H, s, 10’-CH3, 12’-CH3) 3.86 (3H, s, 11’-CH3), 2.72 (1H, d, J = 6.2

Hz, 8-H), 2.29–2.12 (2H, m, -CH2-), 1.76 (3H, s, 12-CH3), 1.71–1.64 (2H, m, -CH2-),

1.30 (3H, s, 10-CH3), 1.26 (3H, s, 11-CH3); 13C NMR (101 MHz, CDCl3), δ(ppm): 167.0,

153.4 (+), 144.8, 141.6, 130.0, 118.9 (+), 117.4 (+), 105.1 (+), 64.0 (+), 61.4 (s, 3-C),

58.5, 56.1 (+), 36.3 (-), 27.1 (-), 24.9 (+), 18.8 (+), 16.6 (+); GC: Rt= 26.167 min, MS

(EI), m/z (%): 390 (M+·, 45), 241 (100), 109 (80), 69 (68), 67 (77), 43 (76); HRMS

(ESI+): m/z: calcd for C22H31O6 ([M+H]+) 391.2115, found: 391.2119; calcd for

C22H30NaO6 ([M+Na]+) 413.1935, found: 413.1938.

4. Characterization data of all synthesized (8-hydroxy-9,9-dimethyl-5-methylene

cyclohexyl)methyl esters 14a-14h

(8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)mehtyl acetate (14a): Colorless oil

(154 mg, 0.725 mmol, 61% yield), Obtained as a mixture of two isomers (14a:15a =

84:16); Rf: [hexane-OEtAc 15:2] = 0.3; IR (ATR, cm-1): 3429 (OH), 2941 (CH), 1729

(C=O), 1612 (C=C), 1233 (C-O), 899 (C=C-H); Spectroscopy NMR data for the major

isomer 14a: 1H NMR (400 MHz, CDCl3), δ(ppm): 5.35–5.30 (1H, m, 4-H), 4.89 (1H, dt, J

= 1.8, 0.9 Hz, 12-Ha), 4.80–4.79 (1H, m, 12-Hb), 4.54 (2H, d, J = 7.1 Hz, -CH2-), 3.99

(1H, t, J = 6.4 Hz, 8-H), 2.13–2.03 (2H, m, -CH2-), 2.00 (3H, s, 2’-CH3), 1.68 (3H, s,

CH3-2), 1.67 (3H, s, CH3-1), 1.65–1.59 (2H, m, -CH2-); 13C NMR (101 MHz, CDCl3),

δ(ppm): δ 171.2, 147.4, 142.0, 118.5 (+), 111.1 (-), 75.4 (+), 61.4 (-), 35.5 (-), 32.8 (-),

21.0 (+), 17.5 (+), 16.5 (+); GC: Rt= 44.281 min, MS (EI), m/z (%): 212 (M+·, 12), 196

(84), 86 (70), 59 (100), 43 (40); HRMS (ESI+): m/z: calcd for C12H21O3 ([M+H]+)

213.1485, found: 213.1487; calcd for C12H20NaO3 ([M+Na]+) 235.1305, found:

235.1301.

(8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl benzoate (14b): Pale yellow

oil (176 mg, 0.681 mmol, 57 % yield), Obtained as a mixture of two isomers (14b:15b =

86:14); Rf: [hexane-OEtAc 15:2] = 0.4; IR (ATR, cm-1): 3433 (OH), 2941 (CH), 1713

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-13

(C=O), 1602 (C=C), 1269 (C-O), 710 (C=C-H); Spectroscopy NMR data for the major

isomer 14b: 1H NMR (400 MHz, CDCl3), δ(ppm): 8.05–8.02 (2H,m, 3’-HAr, 4’-HAr),

7.56–7.50 (m, 1H, 7’-HAr), 7.44–7.39 (2H, m, 5’-HAr, 6’-HAr), 5.52–5.47 (1H, m, 4-H),

4.93 (1H, dt, J = 1.8, 0.9 Hz, 12-Ha), 4.84 (1H, s, -CH2-), 4.83 (1H, d, J = 1.6 Hz, 12-

Hb), 4.82–4.82 (1H, m, -CH2-), 4.05 (1H, t, J = 6.5 Hz, 8-H), 2.19–2.02 (2H, m, -CH2-),

1.92–1.92 (1H, m, OH), 1.77 (3H, s, CH3-2), 1.72 (3H, dd, J = 1.5, 0.9 Hz, CH3-1),

1.70–1.65 (2H, m, -CH2-); 13C NMR (101 MHz, CDCl3), δ(ppm): 166.7, 147.3, 142.1,

132.9 (+), 130.4, 129.6 (+), 128.3 (+), 118.6 (+), 111.3 (-), 75.5 (+), 61.9 (-), 35.5 (-),

32.7 (-), 17.6 (+), 16.7 (+);COSY Correlation [δH/δH]: 8.05-8.02/7.44-7.39 [3’-HAr, 4’-

HAr/5’-HAr, 6’-HAr], 5.42-5.47/4.84 [4-H/-CH2-], 4.83/1.72 [12-Hb/CH3-1], 4-05/1.70-

1.65 [8-H/-CH2-], 2.19-2.02/1.70-1.65 [-CH2-/-CH2]; HSQC Correlation [δH/δC]: 8.05-

8.02/129.6 [3’-HAr, 4’-HAr/3’-C, 4’-C], 7.56-7.50/132.9 [7’-HAr/7’-C], 7.44-7.39/128.3

[5’-HAr, 6’-HAr/5’-C, 6’-C], 5.52-5.47/118.6 [4-H/4-C], 4.93, 4.83/111.3 [12-Ha, 12-

Hb/12-C], 4.84, 4.82/61.9 [-CH2-/3-C], 4.05/75.5 [8-H/8-C], 2.19-2.02/35.5 [-CH2-/6-

C], 1.77/16.7 [CH3-2/CH3-2], 1.72/ 17.6 [CH3-1/CH3-1], 1.70-1.65/32.7 [-CH2-/7-C];

GC: Rt= 44.281 min, MS (EI), m/z (%): 274 (M+·, 14), 196 (84), 86 (70), 59 (100), 43

(40); HRMS (ESI+): m/z: calcd for C17H23O3 ([M+H]+) 275.1642, found: 275.1645;

calcd for C17H22NaO3 ([M+Na]+) 297.1461, found: 297.1458.

(8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 2-chlorobenzoate (14c): Pale

yellow oil (192 mg, 0.621 mmol, 59% yield), Obtained as a mixture of two isomers

(14c:15c = 76:24); Rf: [hexane-OEtAc 15:2] = 0.4; IR (ATR, cm-1): 3399 (OH), 2941

(CH), 1714 (C=O), 1592 (C=C), 1247 (C-O), 1119 (C-O), 721 (C=C-H); Spectroscopy NMR

data for the major isomer 14c: 1H NMR (400 MHz, CDCl3), δ(ppm): 7.79 (1H, dd, J = 7.7,

1.7 Hz, 4’-HAr), 7.42–7.37 (2H, m, 6’-HAr, 7’-HAr), 7.31–7.27 (1H, m, 5’-HAr), 5.51–

5.47 (1H, m, 4-H), 4.93–4.92 (1H, m, 12-Ha), 4.84 (3H, m, 12-Hb, -CH2-), 4.04 (1H, t, J

= 6.4 Hz, 8-H), 2.18–2.02 (2H, m, -CH2-), 1.83 (1H, s, OH), 1.76 (3H, s, CH3-1), 1.71

(3H, s, CH3-2), 1.66 (2H, ddd, J = 9.2, 5.8, 3.0 Hz, -CH2-); 13C NMR (101 MHz,

CDCl3), δ(ppm): δ 165.8, 147.3, 142.7, 132.5 (+), 131.4 (+), 131.0, 126.6, 118.2 (+), 111.3

(-), 75.4 (+), 62.4 (-), 35.5 (-), 32.7 (-), 17.6 (+), 16.7 (+); GC: Rt= 42.382 min, MS (EI),

m/z (%): 308 (M+·, 21), 256 (100), 105 (32), 135 (27), 77 (84), 66 (30); HRMS (ESI+):

m/z: calcd for C17H22ClO3 ([M+H]+) 309.1252, found: 309.1254; calcd for

C17H21ClNaO3 ([M+Na]+) 331.1071, found: 331.1075.

(8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl nicotinate (14d): Pale orange

oil (162 mg, 0.586 mmol, 62% yield), Rf: [hexane-OEtAc 15:3] = 0.3; IR (ATR, cm-1):

3375 (OH), 2941 (CH), 1720 (C=O), 1592 (C=C), 1278 (C-O), 741 (C=C-H); 1H NMR

(400 MHz, CDCl3), δ(ppm): 9.20 (1H, dd, J = 2.1, 0.7 Hz, 4’-HAr), 8.75 (1H, dd, J = 4.9,

1.7 Hz, 7’-HAr), 8.28 (1H, dt, J = 8.0, 2.0 Hz, 3’-HAr), 7.38 (1H, ddd, J = 8.0, 4.9, 0.9

Hz, 5’-HAr), 5.51–5.46 (1H, m, 4-H), 4.93 (1H, dt, J = 1.7, 0.8 Hz, 12-Ha), 4.86 (2H, d,

J = 7.2 Hz, -CH2-), 4.84-4.82 (1H, m, 12-Hb), 4.04 (1H, t, J = 6.4 Hz, 8-H), 2.16–2.06

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García, Puerto & Kouznetsov ESI-14

(2H, m, -CH2-), 1.91 (1H, s, OH), 1.77 (3H, s, CH3-2), 1.72 (3H, s, CH3-1), 1.69–1.64

(2H, m, -CH2-); 13C NMR (101 MHz, CDCl3), δ(ppm): 165.4, 153.3 (+), 150.9 (+), 147.4,

142.9, 137.2 (+), 126.4, 123.4 (+), 118.1 (+), 111.3 (-), 75.4 (+), 62.3 (-), 35.5 (-), 32.8 (-

), 17.6 (+), 16.7 (+);COSY Correlation [δH/δH]: 9.20/8.28 [4’-HAr/3’HAr], 8.75/7.38/8.28

[7’-HAr/5’-HAr/3’-HAr], 8.28/7.38 [3’-HAr/5’-HAr], 5.51-5.46/1.77/4.86 [4-H/CH3-2/-

CH2-], 4.93/1.72 [12-Ha/CH3-1], 4.04/1.69-1.64 [8-H/-CH2-], 2.16-2.06/1.69-1.64 [-

CH2-/-CH2-]; HMBC Correlation [δH/δC]: 9.20/126.4/137.2/153.3 [4’-HAr/2’-C/3’-C/7’-

C], 8.75/123.4 [7’-HAr/5’-C], 8.28/150.9/153.3 [3’-HAr/4’-C/7’-C], 7.38/126.4 [5’-

HAr/2’-C], 5.51-5.46/16.7/35.5 [4-H/CH3-1/6-C], 4.93/17.6/75.4 [12-Ha/CH3-2/8-C],

4.86/118.1/142.9 /165.4 [-CH2-/4-C/9-C/1-C], 4.04/17.6/111.3 [8-H/CH3-2/12-C], 2.16-

2.06/16.7/17.6/32.8/118.1/142.9 [-CH2-/CH3-2/CH3-1/7C/4C/9C], 1.77/16.7/35.5/118.1

/142.9 [CH3-2/CH3-1/6-C/4-C/9-C], 1.72/17.6/75.4/111.3/147.4 [CH3-1/CH3-2/8-C/12-

C/5-C], 1.69-1.64/35.5/75.4/142.9/147.4 [-CH2-/6-C/8-C/9-C/5-C]; NOESY Correlation

[δH/δH]: 8.75/7.38 [7’-HAr/5’-HAr], 8.28/7.38 [3’-HAr/5’-HAr], 5.51-5.46/1.69-1.64/

1.77/2.16-2.06/4.86/4.84-4.82 [4-H/-CH2-/CH3-2/-CH2-/-CH2-/12-Hb], 4.93/4.04 [12-

Ha/8-H], 4.86/1.72/1.77 [-CH2-/CH3-1/CH3-2], 4.04/1.69-1.64 [8-H/-CH2-]. 2.16-

206/1.69-1.64 [-CH2-/-CH2-]; GC: Rt= 43.239 min, MS (EI), m/z (%): 275 (M+·, 19), 217

(100), 189 (48), 136 (61), 122 (20), 78 (86); HRMS (ESI+): m/z: calcd for C16H22NO3

([M+H]+) 276.1594, found: 276.1598; calcd for C16H21NNaO3 ([M+Na]+) 298.1414,

found: 298.1410.

(8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3-phenylpropanoate (14e):

Yellow oil (197 mg, 0.653 mmol, 55% yield), Obtained as a mixture of two isomers

(14e:15e = 80:20); Rf: [hexane-OEtAc 15:2] = 0.4; IR (ATR, cm-1): 3436 (OH), 2920

(CH), 1726 (C=O), 1159 (C-O), 1076 (C-O), 731 (C=C-H); Spectroscopy NMR data for the

major isomer 14e: 1H NMR (400 MHz, CDCl3), δ(ppm): 7.30–7.26 (2H, m, 5’-HAr, 6’-

HAr), 7.19 (3H, dt, J = 4.0, 2.8 Hz, 7’-HAr, 8’-HAr, 9’-HAr), 5.34 (1H, td, J = 7.1, 1.3 Hz,

4-H), 4.95–4.94 (1H, m, 12-Ha), 4.86–4.85 (1H, m, 12-Hb), 4.59 (2H, d, J = 7.0 Hz, -

CH2-), 4.04 (1H, t, J = 6.5 Hz, 8-H), 2.97–2.92 (2H, m, 3’-H), 2.65–2.61 (2H, m, 2’-H),

2.13–2.03 (2H, m, -CH2-), 1.73 (3H, s, CH3-2), 1.70 (3H, s, CH3-1), 1.69–1.64 (2H, m, -

CH2-), 1.58 (1H, s, OH); 13C NMR (101 MHz, CDCl3), δ(ppm): 172.9, 147.3, 142.0,

140.5, 128.50 (+), 128.3 (+), 118.5 (+), 111.2 (-), 75.5 (+), 61.3 (-), 35.9 (-), 35.4 (-),

32.7 (-), 30.9 (-), 17.6 (+), 16.5 (+); GC: Rt= 36.198 min, MS (EI), m/z (%): 302 (M+·,

11), 284 (100), 163 (41), 105 (80), 77 (32); HRMS (ESI+): m/z: calcd for C19H27O3

([M+H]+) 303.1955, found: 303.1958; calcd for C19H26NaO3 ([M+Na]+) 325.1774,

found: 325.1772.

(8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3-(4-

methoxyphenyl)propanoate (14f): Yellow oil (184 mg, 0.552 mmol, 54% yield),

Obtained as a mixture of two isomers (14f:15f = 67:23); Rf: [hexane-OEtAc 15:2] = 0.3;

IR (ATR, cm-1): 3434 (OH), 2942 (CH), 1713 (C=O), 1269 (C-O), 1111 (C-O), 710

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-15

(C=C-H); Spectroscopy NMR data for the major isomer 14e: 1H NMR (400 MHz, CDCl3),

δ(ppm): 7.36-7.32 (2H, m, 5’-HAr, 6’-HAr), 7.25 (2H, dt, J = 4.1, 2.7 Hz, 7’-HAr, 8’-HAr),

5.39 (1H, td, J = 7.1, 1.3 Hz, 4-H), 5.00–4.99 (1H, m, 12-Ha), 4.91–4.90 (1H, m, 12-

Hb), 4.64 (2H, d, J = 7.0 Hz, -CH2-), 4.10 (1H, t, J = 6.5 Hz, 8-H), 3.02–2.98 (2H, m, -

CH2-), 2.70–2.66 (2H, m, -CH2-), 2.18–2.08 (2H, m, -CH2-), 1.78 (3H, s, CH3-2), 1.75

(3H, s, CH3-1), 1.73–1.69 (2H, m, -CH2-), 1.64 (1H, s, OH).; 13C NMR (101 MHz,

CDCl3), δ(ppm): δ 173.4, 147.7, 142.4, 140.9, 128.7 (+), 126.6 (+), 118.9 (+), 111.7 (-),

75.9 (+), 61.8 (-), 55.3 (+) 36.3 (-), 35.8 (-), 33.1 (-), 31.4 (-), 18.0 (+), 16.9 (+); GC: Rt=

38.732 min, MS (EI), m/z (%): 332 (M+·, 17), 315 (100), 246 (28); 193 (68), 135 (88);

HRMS (ESI+): m/z: calcd for C20H29O4 ([M+H]+) 333.2060, found: 333.2057; calcd for

C20H28NaO4 ([M+Na]+) 355.1880, found: 355.1882.

(8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl cinnamate (14g): Yellow oil

(182 mg, 0.605 mmol, 51% yield), Obtained as a mixture of three isomers (14g:15g:17a

= 56:4:39); Rf: [hexane-OEtAc 15:2] = 0.4; IR (ATR, cm-1): 3437 (OH), 2941 (CH),

1708 (C=O), 1636 (C=C), 1164 (C-O), 1071 (C-O) , 704 (C=C-H); Spectroscopy NMR data

for the major isomer 14g: 1H NMR (400 MHz, CDCl3), δ(ppm): 7.69 (1H, d, J = 16.0 Hz,

2’-H), 7.51 (2H, dt, J = 4.7, 3.0 Hz, 5’-HAr, 6’-HAr), 7.38–7.36 (3H, m, 7’-HAr, 8’-HAr,

9’-HAr), 6.44 (1H, d, J = 16.0 Hz, 3’-H), 5.47–5.43 (1H, m, 4-H), 4.95–4.93 (1H, m, 12-

Ha), 4.85–4.84 (1H, m, 12-Hb), 4.72 (2H, d, J = 7.1 Hz, -CH2-), 4.05 (1H, t, J = 6.7 Hz,

8-H), 2.16–2.04 (2H, m, -CH2-), 1.82 (1H, s, OH), 1.75 (3H, s, CH3-2) 1.73 (3H, s, CH3-

1), 1.70–1.63 (2H, m, -CH2-); 13C NMR (101 MHz, CDCl3), δ(ppm): 167.1, 147.4 (+),

142.2, 140.6, 134.4, 128.9 (+), 128.1 (+), 118.6 (+), 118.1 (-), 111.3 (-), 75.5 (+), 61.5 (-

), 35.5 (-), 32.8 (-), 17.6 (+), 16.6 (+).; GC: Rt= 41.120 min, MS (EI), m/z (%): 300 (M+·,

13), 282 (100), 214 (44), 161 (70), 86 (23), 68 (59); HRMS (ESI+): m/z: calcd for

C19H25O3 ([M+H]+) 301.1798, found: 301.1802; calcd for C19H24NaO3 ([M+Na]+)

323.1618, found: 323.1621.

(8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3,4,5-trimethoxycinnamate

(14h): Yellow oil (207 mg, 0.530 mmol, 45% yield), Obtained as a mixture of three

isomers (14h:15g:17b = 47:15:38); Rf: [hexane-OEtAc 15:2] = 0.4; IR (ATR, cm-1):

3381 (OH), 2940 (CH), 1707 (C=O), 1636 (C=C), 1243 (C-O), 1001 (C-O), 751 (C=C-H);

Spectroscopy NMR data for the major isomer 14h: 1H NMR (400 MHz, CDCl3), δ(ppm):

7.59 (2H, d, J = 15.9 Hz, 2’-H), 6.74 (2H, s, 5’-HAr, 6’-HAr), 6.35 (1H, d, J = 15.9 Hz,

3’-H), 5.47–5.42 (1H, m, 4-H), 5.29 (9H, s, 10’-CH3, 11’-CH3, 12’-CH3), 4.94 (1H, dt, J

= 1.7, 0.8 Hz, 12-Ha), 4.84 (1H, dd, J = 3.0, 1.5 Hz, 12-Hb), 4.71 (2H, d, J = 7.1 Hz, -

CH2-), 4.08–4.00 (1H, m, 8-H), 2.23–2.00 (2H, m, -CH2-), 1.75 (3H, s, CH3-2), 1.72

(3H, s, CH3-1), 1.68–1.61 (2H, m, -CH2-); 13C NMR (101 MHz, CDCl3), δ(ppm): 167.1,

153.4, 147.4 (+), 144.8 (+), 142.1, 130.0, 118.6 (+), 117.4 (+), 111.3 (-), 105.1 (+), 75.5

(+), 61.5 (-), 56.2 (+), 35.6 (-), 32.8 (-), 17.6 (+), 16.6 (+). GC: Rt= 40.173 min, MS (EI),

m/z (%): 390 (M+·, 13), 373 (100), 273 (41), 251 (79), 193 (61), 106 (33); HRMS

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-16

(ESI+): m/z: calcd for C22H31O6 ([M+H]+) 391.2115, found: 391.2117; calcd for

C22H30NaO6 ([M+Na]+) 413.1935, found: 413.1932.

5. Extraction and characterization of the essential oil of palmarosa (Cymbopogon

martinii)

The essential oil (EO) of palmarosa was obtained by hydrodistillation from the dried

leaves and stems of Cymbopogon martini in 0.4 ± 0.2% yield with a pale yellow color

and with a citric odor. The main compounds were geraniol (83,9 %) and the geranil

acetate (9,2 %), as revealed the obtained cromathogram accurate by GC-FID Figure

ESI1.

Figure ESI 1. Profile (chromatographic pattern) of the secondary metabolites present in the EO

from palmarosa obtained by GC-FID in a GC capillary column DB-5 (60 m).

With geraniol and geranil acetate, other compounds were identified and quantified by

GC-MS using an internal standard (Istd). Their retention times and percentage, in the

98.2% of the Total Ionic Current (TIC), are described in Table ES1.

Table ES1: Compounds detected after hydrodestillation of leaves and stem from C. martini by

GC-FID

Peaka Compound Linear retention

index Percentage, %

1 cis-β-Ocimene 1038 0,5

2 trans-β-Ocimene 1048 1,5

3 Linalool 1102 2,3

4 Geraniol 1264 83,9

5 Geranyl acetate 1380 9,2

6 trans-β-Caryophyllene 1432 0,8 aPeaks detected in the Profile (chromatographic pattern) obtained by GC-FID.

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-17

6. Copies of 1H NMR, 13C NMR, DEPT-135, COSY, HSQC and HMBC charts of the

synthesized (E)-3,7-dimethylocta-2,6-dien-1-yl esters 12a-12p.

Figure ESI 2. 1H-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl acetate 12a

O

O1 3 5 64

78

911 10

12

2'

1.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.4δ (ppm)

WG281H WG 78 en CDCl3

4-H (td)5.32

J(0.97, 7.09)

8-H (td)5.05

J(1.04, 6.74)

3-H (d)4.56

J(7.15)

2'-H (s)2.03

7-H 6-H (m)2.06

12-H (s)1.67

10-H (s)1.65

11-H (s)1.57

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-18

Figure ESI 3. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl acetate 12a

Figure ESI 4. 1H-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl (E)-3,7-dimethylocta-2,6-dienoate 12b

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-19

Figure ESI 5. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl (E)-3,7-dimethylocta-2,6-dienoate 12b

Figure ESI 6. 1H-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl 5-(1,2-dithiolan-3-yl)pentanoate 12c

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-20

Figure ESI 7. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl 5-(1,2-dithiolan-3-yl)pentanoate 12c

Figure ESI 8. DEPT-135 spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl 5-(1,2-dithiolan-3-yl)pentanoate 12c

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-21

Figure ESI 9. 1H-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl benzoate 12d

Figure ESI 10. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl benzoate 12d

O

O1 3 5 64

78

911 10

12

2'

4'7'

3'5'

6'

102030405060708090100110120130140150160170f1 (ppm)

WG3313C WG33 en CDCl3

12-C (s)16.67

11-C (m)17.82

10-C (s)25.79

6-C (s)39.64

3-C (s)62.01

4-C (s)118.35

8-C (s)123.75

5'-C, 6'-C (m)128.42

3'-C, 4'-C (s)129.60

1-C (s)166.83

5-C (s)142.51

7'-C (s)132.84

9-C (s)131.96

2'-C (s)130.56

7-C (s)26.37

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-22

Figure ESI 11. DEPT-135 spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl benzoate 12d

Figure ESI 12. 1H-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl-2-chlorobenzoate 12e

O

O1 3 5 64

78

911 10

12

2'

4'7'

3'5'

6'

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-23

Figure ESI 13. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl-2-chlorobenzoate 12e

Figure ESI 14. 1H-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl 2-hydroxybenzoate 12f

O

O1 3 5 64

78

911 10

12

OH

2'

4'7'

6'

3'

5'

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-24

Figure ESI 15. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl 2-hydroxybenzoate 12f

Figure ESI 16. 1H-NMR spectrum (E)-3,7-dimethylocta-2,6-dien-1-yl 4-hydroxy-3-methoxybenzoate 12g

16.2

2

17.6

3

25.6

226.1

1

39.3

1

62.1

7

77.1

6 C

hlo

rofo

rm-d

112.0

1

117.4

2117.6

9119.4

0

123.7

5

126.4

6

130.6

4

131.5

8132.1

3

133.7

5136.2

7

142.7

9

149.5

7

162.0

4

164.5

7

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-25

Figure ESI 17. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl 4-hydroxy-3-methoxybenzoate 12g

Figure ESI 18. DEPT-135 spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl 4-hydroxy-3-methoxybenzoate 12g

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-26

Figure ESI 19. 1H-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl nicotinate 12h

Figure ESI 20. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl nicotinate 12h

N

O

O1 3 5 64

78

911 10

12

2'

4'7'

3'5'

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5δ (ppm)

WG81H WG27 en CDCl3

3-H (d)4.85

J(7.13)

4-H (td)5.45

J(1.20, 7.15)

8-H (m)5.06

7-H 6-H (m)2.09

7'-H (dd)8.74

J(1.73, 4.85)

3'-H (m)8.28

5'-H (ddd)7.36

J(0.84, 4.86, 7.95)

4'-H (dd)9.21

J(0.69, 2.12)12-H (s)

1.75

10-H (s)1.65

11-H (s)1.58

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-27

Figure ESI 21. DEPT-135 spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl nicotinate 12h

Figure ESI 22. COSY spectrum of of (E)-3,7-dimethylocta-2,6-dien-1-yl nicotinate 12h

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-28

Figure ESI 23. HSQC spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl nicotinate 12h

Figure ESI 24. HMBC spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl nicotinate 12h

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-29

Figure ESI 25. 1H-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl-2-phenylacetate 12i

Figure ESI 26. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl-2-phenylacetate 12i

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-30

Figure ESI 27. DEPT-135 spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl-2-phenylacetate 12i

Figure ESI 28. 1H-NMR spectrum of (±)-(E)-3,7-dimethylocta-2,6-dien-1-yl 2-hydroxy-2-phenylacetate 12j

3.5

6

2.8

22.9

8

4.7

0

0.3

3

0.4

0

0.9

6

0.1

3

1.9

9

0.1

6

1.1

3

1.0

0

0.0

6

0.9

1

1.5

6

1.6

2

1.6

41.9

6

1.9

8

1.9

8

2.0

0

2.0

3

2.0

5

2.0

7

2.0

9

2.7

0

4.0

74.0

7

4.0

9

4.0

95.0

4

5.0

4

5.0

4

5.0

5

5.0

55.0

5

5.0

6

5.0

6

5.0

6

5.0

7

5.0

7

5.0

8

5.3

4

5.3

4

5.3

5

5.3

5

5.3

6

5.3

65.3

7

5.3

7

5.8

9

7.2

0

7.2

1

7.2

2

7.2

3

7.2

4

7.2

57.2

5

7.2

6

7.2

6 C

hlo

rofo

rm-d

7.2

7

7.2

8

7.2

9

7.3

0

7.3

17.3

1

7.3

2

7.3

7

7.3

8

7.3

9

7.3

9

7.4

0

O

O1 3 5 64

78

911 10

12

2'

4'6'

7'

8'

3'5'

OH

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-31

Figure ESI 29. 13C-NMR spectrum of (±)-(E)-3,7-dimethylocta-2,6-dien-1-yl 2-hydroxy-2-phenylacetate 12j

Figure ESI 30. 1H-NMR spectrum (E)-3,7-dimethylocta-2,6-dien-1-yl-3-phenylpropanoate 12k

16.1

117.5

5

25.5

526.3

4

39.4

8

58.9

8

74.7

8

77.1

6 C

hlo

rofo

rm-d

117.4

2

123.9

1127.2

6

127.4

5128.4

3

129.3

1

131.4

6133.7

1

138.8

6

164.1

8

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-32

Figure ESI 31. 13C-NMR spectrum (E)-3,7-dimethylocta-2,6-dien-1-yl-3-phenylpropanoate 12k

Figure ESI 32. 1H-NMR spectrum (E)-3,7-dimethylocta-2,6-dien-1-yl-3-(4-methoxyiphenyl)propanoate 12l

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-33

Figure ESI 33. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl-3-(4-methoxyiphenyl)propanoate 12l

Figure ESI 34. DEPT-135 spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl-3-(4-methoxyiphenyl)propanoate 12l

O

O1 3 5 64

78

911 10

12

2'

4'

6'

7'

8'9'

3'5'

O10'

O

O1 3 5 64

78

911 10

12

2'

4'

6'

7'

8'9'

3'5'

O10'

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-34

Figure ESI 35. 1H-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl cinnamate 12m

Figure ESI 36. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl cinnamate 12m

O

O1 3 5 64

78

911 10

12

2'

4'

6'

7'

8'

9'

3'5'

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-35

Figure ESI 37. DEPT-135 spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl cinnamate 12m

Figure ESI 38. 1H-NMR spectrum (E)-3,7-dimethylocta-2,6-dien-1-yl (E)-3-(4-hydroxy-3-methoxyphenyl)acrylate 12n

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-36

Figure ESI 39. 13C-NMR spectrum (E)-3,7-dimethylocta-2,6-dien-1-yl (E)-3-(4-hydroxy-3-methoxyphenyl)acrylate 12n

Figure ESI 40. DEPT-135 spectrum (E)-3,7-dimethylocta-2,6-dien-1-yl (E)-3-(4-hydroxy-3-methoxyphenyl)acrylate 12n

O

O1 3 5 64

78

911 10

12

2'

4'

6'

7'

8'9'

3'5'

HO

O10'

102030405060708090100110120130140150160170δ (ppm)

WG3213C WG 74 en CDCl3

12-C (s)16.67

11-C (s)17.84

10-C (s)25.85

7-C (s)26.40

6-C (s)39.70

3-H (s)61.49

1-C (s)167.50

3'-C (s)144.90

5-C (s)142.55

9-C (s)132.01

8-C (s)123.87

4-C (s)118.41

10'-C (s)56.01

8'-C (s)114.80

9'-C (s)147.99

6'-C (s)123.20

7'-C (s)146.83

5'-C (s)109.29

2'-C (s)115.64

4'-C (s)127.12

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-37

Figure ESI 41. 1H-NMR spectrum of (E) 3,7-dimethylocta-2,6-dien-1-yl-(3,4-dimethoxy)cinnamate 12o

Figure ESI 42. 13C-NMR spectrum of (E) 3,7-dimethylocta-2,6-dien-1-yl-(3,4-dimethoxy)cinnamate 12o

O

O1 3 5 64

78

911 10

12

2'

4'

6'

7'

8'9'

3'5'O

O

10'

11'

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0δ (ppm)

WG371H WG37 en CDCl3

10-H (s)1.59

11-H, 12-H (m)1.67

11'-H, 12'-H (d)3.89

J(2.60)

3-H (d)4.14

J(6.94)

8-H (m)5.08

4-H (m)5.40

3'-H (d)6.32

J(15.90)

5'-HAr (d)6.85

J(8.31)

8'-HAr (d)7.04

J(1.91)

6'-HAr (dd)7.09

J(1.93, 8.28)

2'-H (d)7.62

J(15.91)

6-H, 7-H (m)2.06

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-38

Figure ESI 43. DEPT-135 spectrum of ((E)-3,7-dimethylocta-2,6-dien-1-yl-(3,4-dimethoxy)cinnamate 12o

Figure ESI 44. 1H-NMR spectrum (E)-3,7-dimethylocta-2,6-dien-1-yl-(3,4,5-trimethoxy)cinnamate 12p

O

O1 3 5 64

78

911 10

12

2'

4'

6'

7'

8'9'

3'5'O

O

10'

11'

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-39

Figure ESI 45. 13C-NMR spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl-(3,4,5-trimethoxy)cinnamate 12p

Figure ESI 46. DEPT-135 spectrum of (E)-3,7-dimethylocta-2,6-dien-1-yl-(3,4,5-trimethoxy)cinnamate 12p

O

O1 3 5 64

78

911 10

12

2'

4'

6'

7'

8'9'

3'5'O

O

10'

11'

O12'

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-40

7. Copies of 1H NMR, 13C NMR, DEPT-135, COSY, HSQC and HMBC charts of the

synthesized (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl esters 13a-13k.

Figure ESI 47. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl acetate 13a

Figure ESI 48. 13C-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl acetate 13a

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-41

Figure ESI 49. 1H-NMR spectrum of (±)-(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-5-(1,2-dithiolan-3-yl)pentanoate 13b

Figure ESI 50. 13C-NMR spectrum of (±)-(E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-5-(1,2-dithiolan-3-yl)pentanoate 13b

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-42

Figure ESI 51. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl benzoate 13c

Figure ESI 52. 13C-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl benzoate 13c

O

O

O

1 34

5 6

7

8

9

10

12

4'7'

11

2'

3'

5'

6'

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5δ (ppm)

WG411H WG41 en CDCl3

3'-H, 4'-H (dt)8.04

J(1.76, 8.49)

7'-H (m)7.54

5'-H, 6'-H (m)7.42

4-H (td)5.51

J(1.19, 7.00)

3-H (d)4.84

J(7.00)

8-H (t)2.71

J(6.26)

6-H (m)2.21

12-H (s)1.78

7-H (m)1.68

10-H (s)1.29

11-H (s)1.26

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-43

Figure ESI 53. DEPT-135 spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl benzoate 13c

Figure ESI 54. COSY spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl benzoate 13c

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-44

Figure ESI 55. HSQC spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl benzoate 13c

Figure ESI 56. HMBC spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl benzoate 13c

O

O

O

1 34

5 6

7

8

9

10

12

4'7'

11

2'

3'

5'

6'

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5δ (ppm)

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

WG41HMBC WG41 en CDCl3

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-45

Figure ESI 57. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl nicotinate 13d

Figure ESI 58. 13C-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl nicotinate 13d

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-46

Figure ESI 59. DEPT-135 spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl nicotinate 13d

Figure ESI 60. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-2-chlorobenzoate 13e

N

O

O

O

1 34

5 6

7

8

9

10

12

4'7'

11

2'

3'

5'

102030405060708090100110120130140150δ (ppm)

RMNDEPT135 WG34 en CDCl3

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-47

Figure ESI 61. 13C NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-2-chlorobenzoate 13e

Figure ESI 62. DEPT-135 spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-2-chlorobenzoate 13e

O

O

O

1 34

5 6

7

8

9

10

12

4'7'

11

2'

3'

5'

6'

Cl

101520253035404550556065707580859095100105110115120125130135140δ (ppm)

WG10DEPT135 WG60 en CDCl3

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-48

Figure ESI 63. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-2-phenylacetate 13f

Figure ESI 64. 13C-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-2-phenylacetate 13f

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-49

Figure ESI 65. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-3-phenylpropanoate 13g

Figure ESI 66. 13C-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-3-phenylpropanoate 13g

O

O

O

1 34

5 6

7

8

9

10

12

11

2'

4'

6'

7'

9'

8'

3'5'

1.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.07.27.47.6δ (ppm)

WG131H WG49 en CDCl3

4-H (td)5.35

J(1.22, 7.08)

3-H (d)4.59

J(7.07)

3'-H (t)2.95

J(7.85)

8-H (t)2.70

J(6.25)

2'-H (m)2.63

7'-H, 8'-H, 9'-H (m)7.19

5'-H, 6'-H (t)7.28

J(5.17)

6-H (m)2.18

7-H (td)1.65

J(3.75, 7.91)

12-H (s)1.71

10-H (s)1.30

11-H (s)1.26

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-50

Figure ESI 67. DEPT-135 spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-3-phenylpropanoate 13g

Figure ESI 68. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-3-(4-methoxypheny)lpropanoate 13h

O

O

O

1 34

5 6

7

8

9

10

12

11

2'

4'

6'

7'

9'

8'

3'5'

101520253035404550556065707580859095100105110115120125130135δ (ppm)

WG13DEPT135 WG49 en CDCl3

O

O

O

1 34

5 6

7

8

9

10

12

11

2'

4'

6'

7'

9'

8'

3'5'

O

10'

1.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.07.27.4δ (ppm)

WG57

1H WG57 en CDCl3

7'-H, 8'-H (m)

7.10

5'-H, 6'-H (m)6.81

4-H (m)

5.35

3-H (d)4.58

J(7.05)

10'-H (s)

3.77

2'-C (t)2.88

J(7.79)

8-H (t)2.69

J(6.25)

3'-C (m)

2.58

6-H (m)

2.17

12-C (s)

1.70

7-H (m)1.65

10-H (s)

1.29

11-H (s)1.25

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-51

Figure ESI 69. 13C-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-3-(4-methoxypheny)lpropanoate 13h

Figure ESI 70. DEPT-135 spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-3-(4-methoxypheny)lpropanoate 13h

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-52

Figure ESI 71. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl cinnamate 13i

Figure ESI 72. 13C-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl cinnamate 13i

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-53

Figure ESI 73. DEPT-135 spectrum of (E)-3,7-dimethylocta-2-en-6,7 epoxy-1-yl cinnamate 13i

Figure ESI 74. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-(3,4-trimethoxy)cinnamate 13j

O

O

O

1 34

5 6

7

8

9

10

12

11

2'

4'

6'

7'

9'

8'

3'5'

1520253035404550556065707580859095100105110115120125130135140145150155δ (ppm)

WG5DEPT135 WG18 en CDCl3

O

O

O

1 34

5 6

7

8

9

10

12

11

2'

4'

6'

7'

9'8'

3'5'O

O

10'

11'

1.01.52.02.53.03.54.04.55.05.56.06.57.07.5δ (ppm)

WG141H RMN en CDCl3 WG44

3-H (d)4.82

J(6.20)

4-H (m)5.39

2'-H (d)7.62

J(15.09)

3'-H (d)6.62

J(15.11)

6'-H, 8'-H (m)7.25

5'-H (d)7.06

J(7.70)

10'-H (s)3.84

11'-H (s)3.76

8-H (t)2.23

J(6.02)

6-H (m)2.04

12-H (s)1.77

7-H (m)1.59

10-H (s)1.32

11-H (s)1.19

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-54

Figure ESI 75. 13C-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-(3,4-trimethoxy)cinnamate 13j

Figure ESI 76. 1H-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-(3,4,5-trimethoxy)cinnamate 13k

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-55

Figure ESI 77. 13C-NMR spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-(3,4,5-trimethoxy)cinnamate 13k

Figure ESI 78. DEPT-135 spectrum of (E)-3,7-dimethylocta-2-en-6,7-epoxy-1-yl-(3,4,5-trimethoxy)cinnamate 13k

O

O

O

1 34

5 6

7

8

9

10

12

11

2'

4'

6'

7'

9'8'

3'5'O

O

O

10'

11'

12'

101520253035404550556065707580859095100105110115120125130135140145150δ (ppm)

RMNDEPT135 WG36 en CDCl3

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-56

8. Copies of 1H NMR, 13C NMR, DEPT-135, COSY, HSQC and HMBC charts of the

synthesized (3-hydroxy-2,2-dimethyl-6-methylenecyclohexyl) methyl esters 14a-

14h.

Figure ESI 79. 1H-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)mehtyl acetate 14a

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-57

Figure ESI 80. 13C-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)mehtyl acetate 14a

Figure ESI 81. 1H-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl benzoate 14b

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-58

Figure ESI 82. 13C-NMR spectrum of spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl benzoate 14b

Figure ESI 83. DEPT-135 spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl benzoate 14b

O

O

OH

12a 12b

*14

98

7

6

52'

4'7'

33'

5'

*6'

102030405060708090100110120130140150160170δ (ppm)

WG6613C WG66 en CDCl3

6-C (s)35.55

7-C (s)32.79

8-C (s)75.50

3-C (s)61.93

12-C (s)111.32

4-C (s)118.68

CH3-2 (s)16.70

CH3-1 (s)17.63

7'-C (s)132.94

5'-C, 6'-C (s)128.39

3'-C, 4'-C (s)129.66

1-C (s)166.79

2'-C (s)147.39

5-C (s)142.17

9-C (s)130.45

8-C (s)76.22

6-C (s)50.87

7-C (s)31.43

O

O

OH

12a 12b

*14

98

7

6

52'

4'7'

33'

5'

*6'

1520253035404550556065707580859095100105110115120125130135δ (ppm)

WG66DEPT135 WG66 en CDCl3

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-59

Figure ESI 84. COSY spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl benzoate 14b

Figure ESI 85. HSQC spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl benzoate 14b

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-60

Figure ESI 86. 1H-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 2-chlorobenzoate 14c

Figure ESI 87. 13C-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 2-chlorobenzoate 14c

O

O

OH

12a 12b

*14

98

7

6

52'

4'7'

33'

5'

*6'

Cl

102030405060708090100110120130140150160170δ (ppm)

WG2613C WG 71 en CDCl3

CH3-2 (s)16.71

CH3-1 (s)17.64

7-C (s)32.75

6-C (s)35.52

3-C (s)62.41

8-C (s)75.46

12-C (s)111.35

4-C (s)118.28

2'-C (s)126.64

1-C (s)165.89

5-C (s)147.37

9-C (s)142.77

3'-C, 4'-C (s)132.51

5'-C, 6'-C (s)131.40

7'-C (s)131.08

8-C (s)76.11

6-C (s)50.84

7-C (s)31.43

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-61

Figure ESI 88. 1H-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl nicotinate 14d

Figure ESI 89. 13C-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl nicotinate 14d

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-62

Figure ESI 90. DEPT-135 spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl nicotinate 14d

Figure ESI 91. COSY spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl nicotinate 14d

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-63

Figure ESI 92. HMBC spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl nicotinate 14d

N

O

O

OH

12a 12b

*14

9 87

6

52'

4'7'

33'5'

*

1.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 δ (ppm)

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

180

δ (

ppm

)

WG21HMBC WG67 en CDCl3

Figure ESI 93. NOESY spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl nicotinate 14d

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-64

Figure ESI 94. 1H-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3-phenylpropanoate 14e

Figure ESI 95. 13C-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3-phenylpropanoate 14e

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-65

Figure ESI 96. DEPT-135 spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3-phenylpropanoate 14e

Figure ESI 97. 1H-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3-(4-methoxyphenyl)propanoate 14f

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-66

Figure ESI 98. 13C-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3-(4-methoxyphenyl)propanoate 14f

Figure ESI 99. 1H-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl cinnamate 14g

O

O

OH

12a 12b

*14

98

7

6

52'

33'

*9'

7'

6'8'

5'4'

1.62.02.42.83.23.64.04.44.85.25.66.06.46.87.07.27.47.67.8δ (ppm)

RMN1H WG68 en CDCl3

2'-H (d)7.69

5'-H, 6'-H (m)7.51

7'-H, 8'-H, 9'-H (m)7.37

3'-H (d)6.44

4-H (td)5.45

12a (d)4.95

12b (d)4.84

8-H (t)4.05

6-H (ddd)2.09

OH (m)1.81

CH3-2 (s)1.75

CH3-1 (d)1.73

7-H (m)1.65

3-H (d)4.72

8-H (dd)3.48

2'-H (m)2.94

3'-H (m)2.62

6-H (m)2.43

7-H (m)1.56

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-67

Figure ESI 100. 13C-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl cinnamate 14g

Figure ESI 101. DEPT-135 spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl cinnamate 14g

O

O

OH

12a 12b

*14

98

7

6

52'

33'

*9'

7'

6'8'

5'4'

1520253035404550556065707580859095100105110115120125130135140145150155δ (ppm)

RMNDEPT135 WG68 en CDCl3

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-68

Figure ESI 102. 1H-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3,4,5-trimethoxycinnamate 14h

Figure ESI 103. 13C-NMR spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3,4,5-trimethoxycinnamate 14h

O

O

OH

12a 12b

*14

98

7

6

52'

33'

*9'

7'

6'8'

5'4'O

O

O

10'

11'

12'

1.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.8δ (ppm)

WG201H WG69 en CDCl3

2'-H (d)7.59

J(15.92)

5'-H, 6'-H (s)6.74

3'-H (d)6.35

J(15.90)

10'-H, 11'-H, 12'-H (s)5.29

4-H (m)5.44

6-H (m)2.09

8-H (tt)4.05

J(5.17, 10.31)

3-H (d)4.71

J(7.11)

12-Ha (dt)4.94

J(0.85, 1.73)

12-Hb (dt)4.84

J(1.49, 3.01)

CH3-2 (d)1.75

J(0.91)

CH3-1 (m)1.72

7-H (m)1.64

2'-H (t)2.88

J(7.80)

3'-H (t)2.61

J(7.84)

O

O

OH

12a 12b

*14

98

7

6

52'

33'

*9'

7'

6'8'

5'4'O

O

O

10'

11'

12'

102030405060708090100110120130140150160170δ (ppm)

WG2013C WG69 en CDCl3

1-C (s)167.11

7'-C, 8'-C, 9'-C (s)153.49

2'-C (s)144.83

4'-C (s)130.05

4-C (s)118.64

3'-C (s)117.48

5'-C, 6'-C (s)105.19

3-C (s)61.51

10'-C, 11'-C, 12'-C (s)56.21

CH3-1 (s)17.69

CH3-2 (s)16.69

6-C (s)35.60

7-C (s)32.83

8-C (s)75.58

9-C (s)142.18

12-C (s)111.35

5-C (s)147.42

3'-C (s)36.16

2'-C (s)31.48

Gd-Catalyzed the Synthesis of Geranyl Esters for their Radical Cyclization. Electr. Supp. Inform.

García, Puerto & Kouznetsov ESI-69

Figure ESI 104. DEPT-135 spectrum of (8-hydroxy-9,9-dimethyl-5-methylene cyclohexyl)methyl 3,4,5-trimethoxycinnamate 14h